EP0072347A1 - N-phenylsulfonyl-N'-pyrimidinyl and -triazinyl ureas - Google Patents

N-phenylsulfonyl-N'-pyrimidinyl and -triazinyl ureas Download PDF

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Publication number
EP0072347A1
EP0072347A1 EP82810323A EP82810323A EP0072347A1 EP 0072347 A1 EP0072347 A1 EP 0072347A1 EP 82810323 A EP82810323 A EP 82810323A EP 82810323 A EP82810323 A EP 82810323A EP 0072347 A1 EP0072347 A1 EP 0072347A1
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formula
alkyl
halogen
alkenyl
radical
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German (de)
French (fr)
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EP0072347B1 (en
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Willy Meyer
Werner Dr. Föry
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/48—Two nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/56—One oxygen atom and one sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/42—One nitrogen atom
    • C07D251/46—One nitrogen atom with oxygen or sulfur atoms attached to the two other ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D521/00—Heterocyclic compounds containing unspecified hetero rings

Definitions

  • the present invention relates to new, herbicidally active and plant growth-regulating N-phenylsulfonyl-N'-pyrimidinyl- and -triazinylureas, processes for their preparation, agents containing them as active compounds, and their use for controlling weeds, especially selectively in crops or for regulating and inhibiting plant growth:
  • Urea compounds, triazine compounds and pyrimidine compounds with herbicidal activity are generally known.
  • Arylsulfamoyl-heterocyclyl-aminocarbamoyl compounds with herbicidal and plant growth-regulating activity have recently been disclosed, for example in Dutch patent 121 788, European patent publications No. 9419, 23422, US patent No. 4 127 405, in DT-OS 2,715,786 or in FR-PS 1 468 747.
  • alkyl is to be understood as straight-chain or branched alkyl; e.g .: methyl, ethyl, n-propyl, i-propyl, the four isomeric butyl, n-amyl, i-amyl, 2-amyl, 3-amyl, n-hexyl or i-hexyl.
  • Alkoxy is to be understood as: methoxy, ethoxy, n-propyloxy, i-propyloxy and the four isomeric butyloxy radicals, but especially methoxy, ethoxy or i-propoxy.
  • alkylthio examples include methylthio, ethylthio, n-propylthio, i-propylthio and n-butylthio, but especially methylthio and ethylthio.
  • alkenyl radicals are vinyl, allyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-isobutenyl, 2-isobutenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl and 4-pentenyl, but especially vinyl, allyl and 4-pentenyl.
  • alkylsulfinyl examples include methylsulfinyl, ethylsulfinyl, n-propylsulfinyl and n-butylsulfinyl, but especially methylsulfinyl and ethylsulfinyl.
  • alkylsulfonyl examples include methylsulfonyl, ethylsulfonyl, n-propylsulfonyl and n-butylsulfonyl, but especially methylsulfonyl and ethylsulfonyl.
  • Halogen in the definitions and in haloalkyl, alkoxy, alkylsulfinyl, alkylsulfonyl and alkylthio are to be understood as fluorine, chlorine and bromine, but preferably fluorine and chlorine.
  • Preferred haloalkyl radicals which can also be constituents of larger substituent groups, such as e.g. of a haloalkoxy or haloalkylthio radical are difluoromethyl, trifluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, chlorofluoromethyl, bromofluoromethyl, 2-chloroethyl, 1,1,2,2-tetrafluoroethyl, 2-fluoroethyl, 2,2,2-trichloroethyl , Bromodifluoromethyl, chlorodifluoromethyl, 1,1,2-trifluoro-2-chloroethyl, 1,1,2-trifluoro-2-bromoethyl, 1,1,2,3,3,3-hexafluoropropyl, but especially difluoromethyl, 2.2 , 2-trifluoroethyl and perfluoroethyl.
  • Alkynyl radicals in the definitions of the above symbols generally correspond to propargyl, 2-butynyl, 3-butynyl, and isomeric pentynyl or hexynyl radicals, but the alkynyl radical is preferably embodied by propargyl or 2- or 3-butynyl.
  • the invention also encompasses the salts which the compounds of the formula I can form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.
  • alkali and alkaline earth metal hydroxides as salt formers, the hydroxides of lithium, sodium, potassium, magnesium or calcium should be emphasized, but especially those of sodium or potassium.
  • amines suitable for salt formation are primary, secondary and tertiary aliphatic and aromatic amines such as methylamine, ethylamine, propylamine, i-propylamine, the four isomeric butylamines, dimethylamine, diethylamine, diethanolamine, dipropylamine, diisopropylamine, di-n-butylamine, pyrrolidine, Piperidine, morpholine, trimethylamine, triethylamine, tripropylamine, quinuclidine, pyridine, quinoline and i-quinoline, but especially ethyl-, propyl-, diethyl- or triethylamine, but especially isopropylamine and diethanolamine.
  • primary, secondary and tertiary aliphatic and aromatic amines such as methylamine, ethylamine, propylamine, i-propylamine, the four isomeric butylamines, dimethylamine, die
  • Examples of quaternary ammonium bases are generally the cations of halogen ammonium salts, e.g. the tetramethylammonium cation, the trimethylbenzylammonium cation, the triethylbenzylammonium cation, the tetraethylammonium cation, the trimethylethylammonium cation, but also the ammonium cation.
  • halogen ammonium salts e.g. the tetramethylammonium cation, the trimethylbenzylammonium cation, the triethylbenzylammonium cation, the tetraethylammonium cation, the trimethylethylammonium cation, but also the ammonium cation.
  • X and Z are oxygen and m is the number one and the radical -X-A occupies the ortho position 'to the sulfonyl group.
  • R 4 represents halogen ethoxy and halogen methoxy.
  • R 4 is the 2,2,2-trifluoroethoxy radical or the difluoromethoxy radical.
  • the compounds of the formula I are prepared in an inert, organic solvent.
  • the compounds of formula I are obtained by using a phenylsulfonamide of formula II wherein A, R 1 , R 2 , X and m have the meaning given under formula I, in the presence of a base with an N-pyrimidinyl or triazinyl carbamate of the formula III wherein E, R 3 , R 4 and Z have the meaning given under formula I, and R 11 represents hydrogen, halogen, nitro or C 1 -C 3 alkyl.
  • a second process gives compounds of the formula I by using a phenylsulfonyl isocyanate or isothiocyanate of the formula IV wherein A, R 1 , R 2 , m, X and Z have the meaning given under formula I, optionally in the presence of a base, with an amine of formula V. in which E, R 3 and R 4 have the meaning given under formula I.
  • the compounds of the formula I are prepared by, if appropriate in the presence of a base, a sulfonamide of the above formula III with an isocyanate or isothiocyanate of the formula VI in which E, R 3 , R 4 and Z have the meaning given under formula I.
  • the compounds of the formula I can also be obtained by using an N-phenylsulfonylcarbamate of the formula VII in which A, R 1 , R 2 , m and X have the meaning given under formula I and R 11 represents aeric, halogen, nitro or C 1 -C 3 -alkyl, reacted with an amine of formula V given above.
  • the ureas of the formula I obtained can be converted into addition salts using amines, alkali metal or alkaline earth metal hydroxides or quaternary ammonium bases. This is done, for example, by reacting with the equimolar amount of base and evaporating the solvent.
  • the reactions to compounds of formula I are advantageously carried out in aprotic, inert, organic solvents such as methylene chloride, tetrahydrofuran, acetonitrile, dioxane, toluene.
  • organic bases such as amines such as triethylamine, quinuclidine, quinoline, pyridine etc.
  • inorganic bases such as hydrides such as sodium or calcium hydride, hydroxides such as sodium and potassium hydroxide, carbonates such as sodium and potassium carbonate or hydrogen carbonates such as potassium and Sodium bicarbonate can be used.
  • the reaction temperatures are preferably between -20 ° and + 120 ° C.
  • the reactions are generally slightly exothermic and can be carried out at room temperature.
  • the mixture is expediently warmed up briefly to the boiling point of the reaction mixture.
  • the end products can be isolated by concentrating and / or evaporating the solvent and can be purified by recrystallizing or triturating the solid residue in solvents in which they do not dissolve well, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.
  • the compounds of the formula I are notable for good selective growth-inhibiting and selective herbicidal properties which make them excellent for use in crops of useful plants, in particular in cereals, cotton, soybeans, corn and rice. Weeds are sometimes damaged, which previously could only be dealt with with total herbicides.
  • the compounds of the formula I also have strong plant growth-regulating properties which can have an effect on increasing the yield of crop plants or crops. Many compounds of formula I also show a concentration-dependent plant growth-inhibiting effect. Both monocots and dicots are impaired in their growth.
  • the legumes which are often cultivated in agriculture in tropical regions as "cover crops” are selectively inhibited in their growth by the compounds of the formula I, so that soil erosion between the crop plants is prevented, but the "cover crops” are not Can become competition for culture.
  • An inhibition of vegetative growth allows a denser cultivation of the crop in many crop plants, so that an additional yield, based on the soil area, can be achieved.
  • Another mechanism of increasing yield with growth inhibitors is based on the fact that the nutrients benefit the bloom and fruit formation to a greater extent, while vegetative growth is restricted.
  • the compounds of the formula I are also suitable for preventing the germination of stored potatoes. When potatoes are stored over the winter, germs often develop which result in shrinkage, weight loss and rotting.
  • the invention also relates to herbicidal and plant growth regulating compositions which contain a novel compound of formula I, and to methods for pre- and post-emergent weed control, for inhibiting the growth of monocots and dicots, especially grasses, tro p regard crops and tobacco plant suckers .and to regulate plant growth, especially of legumes.
  • the compounds of the formula I are used in unchanged form or, preferably, as agents together with the auxiliaries customary in formulation technology and are therefore used, for example, to form emulsion concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in eg polymeric materials processed in a known manner.
  • the application methods such as spraying, atomizing, dusting, scattering or pouring, are selected in the same way as the type of agent, in accordance with the desired objectives and the given conditions.
  • formulations ie the agents, preparations or compositions comprising the active ingredient of the formula I and, if appropriate, a solid or liquid additive, are prepared in a known manner, for example by intimately mixing and / or grinding the active ingredients with extenders, for example with solvents, solid carriers, and optionally surface-active compounds (surfactants).
  • extenders for example with solvents, solid carriers, and optionally surface-active compounds (surfactants).
  • Aromatic hydrocarbons preferably fractions C 8 to C 12 , such as xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as Ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.
  • Aromatic hydrocarbons preferably fractions C 8 to C 12 , such as xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic
  • Natural rock flours such as calcite, talc, kaolin, montmorillonite or attapulgite, are generally used as solid carriers, for example for dusts and dispersible powders.
  • Porous types such as pumice, broken brick, sepiolite or bentonite can be used as granular, adsorptive granulate carriers, and non-sorptive carrier materials, such as calcite or sand.
  • a large number of preanulated materials of inorganic or organic nature such as in particular dolomite or comminuted plant residues, can be used.
  • suitable surface-active compounds are nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties.
  • surfactants are also to be understood as mixtures of surfactants.
  • Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.
  • the soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (C 10 -C 22 ), such as, for example Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained, for example, from coconut or tallow oil.
  • the fatty acid methyl taurine salts should also be mentioned.
  • the fatty sulfonates or sulfates are usually present as alkali, alkaline earth or optionally substituted ammonium salts and have an alkyl radical with 8 to 22 carbon atoms, alkyl also including the alkyl part of acyl radicals, e.g. the Na or Ca salt of lignin sulfonic acid, dodecyl sulfate or a fatty alcohol sulfate mixture made from natural fatty acids.
  • This subheading also includes the salts of sulfuric acid esters and sulfonic acids from fatty alcohol / ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain 2-sulfonic acid groups and a fatty acid residue with 8-22 carbon atoms.
  • Alkylarylsulfonates are e.g. the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or a naphthalenesulfonic acid-formaldehyde condensation product.
  • Corresponding phosphates such as e.g. Salts of the phosphoric acid ester of a p-nonylphenol (4-14) ethylene oxide adduct in question.
  • Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols can.
  • nonionic surfactants are the water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain.
  • the compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
  • nonionic surfactants are nonylphenol polyethoxy ethanol, castor oil polyglycol ether, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
  • Fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbita trioleate, are also suitable.
  • the cationic surfactants are primarily quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 carbon atoms as N substituents and have lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl radicals as further substituents.
  • the salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. the stearyltrimethylammonium chloride or the benzyldi (2-chloroethyl) ethylammonium bromide.
  • the pesticidal preparations generally contain 0.1 to 95%, in particular 0.1 to 80%, active ingredient of the formula I, 1 to 99.9% of one solid or liquid additive and 0 to 25%, in particular 0.1 to 25% of a surfactant.
  • the use forms can be diluted down to 0.001% of active ingredient.
  • the application rates are generally 0.01 to 10 kg ai / ha, preferably 0.025 to 5 kg ai / ha.
  • the agents can also contain other additives such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers or other active ingredients to achieve special effects.
  • temperatures are in degrees Celsius, the pressures in millibars mb.
  • Example 1 N- (2-difluoromethoxyphenylsulfonyl) -N '- [4-methoxy-6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] urea.
  • Example 2 N- (2-difluoromethoxyphenylsulfonyl) -N '- (4-difluoromethoxy-6-methyl-pyrimidin-2-yl) urea.
  • Example 3 N- [2- (2-ethoxyethoxy) phenylsulfonyl] -N '- (4-difluoro-methoxy-6-methyl-pyrimidin-2-yl) urea.
  • Example 4 2-Amino-4-difluoromethylthio-6-methoxy-1,3,5-triazine.
  • a suspension of 16.4 g of 2-amino-4,6-dichloropyrimidine in 100 ml of 40% sodium hydroxide solution is stirred at a temperature of 95-100 ° C. for 1 hour.
  • 20 g of gaseous difluorochloromethane are introduced at a temperature of 70-75 ° C. within 1 hour.
  • Concentration to about 1/5 of the volume, pouring into water and separating off the solid precipitate gives 6 g of 2-eimino-4-chloro-6-difluoromethoxy-pyrimidine, mp. 118-119 ° C.
  • Example 8 Formulation examples for active ingredients of the formula I.
  • the active ingredient is mixed well with the additives and ground well in a suitable mill.
  • Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.
  • Emulsions of any desired concentration can be prepared from this concentrate by dilution with water.
  • Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding it in a suitable mill.
  • the active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in an air stream.
  • the finely ground active ingredient is evenly applied in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.
  • the finely ground active ingredient is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
  • Example 9 In the same experimental set-up as in Example 9, a large number of plant seeds are treated with different amounts of active substance. The evaluation is carried out on the same scale.
  • a number of weeds and crops, both monocotyledonous and dicotyledonous, are sprayed after emergence in the 4- to 6-leaf stage with an aqueous active ingredient dispersion in doses of 4 kg AS / ha and then at 24 ° to 26 ° C. and 45-60% relative humidity kept. 15 days after the treatment, the test is evaluated and evaluated on the same scale as in the pre-emergent test.
  • Example 11 In the same experimental setup as in Example 11, a large number of plants are treated with different amounts of active substance. The evaluation is carried out on the scale given in Example 9.
  • Example 13 Detection of the inhibition of germs on stored potatoes.
  • Example 14 Detection of growth inhibition in tropical ground cover legumes (cover crops)
  • Test plants of the cultivars Psophocarpus palustris and Centrosema pubescens from cuttings are grown in plastic trays with a soil-peat-sand mixture (1: 1: 1). After rooting, the plantlets are repotted in 9 cm pots and watered as needed. The plants are further grown in the greenhouse at a day temperature of 27 ° C. and a night temperature of 21 ° C., with an average light duration of 14 h (6000 lux) and a humidity of 70%. The test plants are cut back to a height of approx. 15 cm and sprayed 7 days after cutting back with a spray mixture of the active ingredient (equivalent to 0.3 or 3 kg of active ingredient per hectare).
  • the growth of the treated plants is compared to trimmed but untreated control plants.
  • the plants treated with the active compounds of the formula I showed a significant reduction in new growth (less than 20% of the new growth in untreated control plants) without the test plants being damaged in the process.
  • test plants are sown in sandy-loamy soil in plastic containers with 30 1 content (60x30x25 cm), covered with a 1-2 cm thick layer of soil and watered. After one day, the active ingredient is applied in the form of an aqueous spray mixture in an amount corresponding to 500 l / ha in concentrations corresponding to 60 g / ha and 30 g / ha.
  • the containers are then kept in the greenhouse at temperatures of 20-25 ° C and poured if necessary. After 33 days, the test is evaluated and scored on the same scale as in Example 9.
  • “Hark” soybeans are sown in plastic containers with a 6: 3: 1 soil-peat-sand mixture and placed in a climatic chamber. Through optimal temperature selection, lighting, adding fertilizer and irrigation, the plants develop after about 5 weeks until the 5-6 trifolia leaf stage. At this point, the plants are sprayed with the aqueous broth of an active ingredient of the formula I until thoroughly wetted. The active ingredient concentration is up to 100 g ai / ha. The evaluation takes place about 5 weeks after application of the active ingredient. In comparison to untreated control plants, the active compounds of the formula I according to the invention bring about a noticeable increase in the number and weight of the pods on the main shoot.

Abstract

N-Phenylsulfonyl-N'-pyrmidinyl- und -triazinyl-harnstoffe der allgemeinen Formel <IMAGE> und die Salze dieser Verbindungen mit Aminen, Alkali- oder Erdalkalimetallbasen oder mit quaternären Ammoniumbasen haben gute pre- und postemergent-selektive herbizide und wuchsregulierende Eigenschaften. In dieser Formel bedeuten A einen durch Halogen, C1-C4-Alkoxy, C1-C4-Alkylthio, C1-C4-Alkylsulfinyl, C1-C4-Alkylsulfonyl, C1-C4-Halogenalkoxy, C1-C4-Halogenalkylthio, C1-C4-Halogenalkylsulfinyl oder C1-C4-Halogenalkylsulfonyl substituierten C1-C6-Alkylrest, oder einen durch die aufgezahlten Reste substituierten C2-C6-Alkenylrest, E die Methingruppe oder Stickstoff, X Sauerstoff, Schwefel, eine Sulfinyl- oder Sulfonylbrucke, Z Sauerstoff oder Schwefel, m die Zahl eins oder zwei, R1 Wasserstoff, Halogen, C1-C5-Alkyl, C2-C5-Alkenyl oder einen Rest -Y-R5, R2 Wasserstoff, Halogen, C1-C5-Alkyl, C2-C5-Alkenyl C1-C4-Halogenalkyl, oder einen Rest -Y-R5, -COOR6, -NC oder -CO-NR7-R8, R³ Wasserstoff, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Alkylthio, C1-C4-Halogenalkyl, Halogen, C1-C4-Halogenalkoxy oder Alkoxyalkyl mit höchstens 4 Kohlenstoffatomen, R4 C1-C4-Halogenalkoxy oder C1-C4-Halogenalkylthio, R5 und R6 je C1-C5Alkyl, C3-C5-Alkenyl oder C2-C6-Alkinyl, R7 und R8 unabhängig voneinander Wasserstoff, C1-C5-Alkyl, C2-C5-Alkenyl oder C2-C6-Alkinyl und Y Sauerstoff, Schwefel, eine Sulfinyl- oder Sulfonylbrücke. wobei A auch für den unsubstituierten C2-C6-Alkenylrest steht kann wenn gleichzeitig X Sauerstoff bedeutet.N-phenylsulfonyl-N'-pyrmidinyl- and -triazinyl-ureas of the general formula <IMAGE> and the salts of these compounds with amines, alkali metal or alkaline earth metal bases or with quaternary ammonium bases have good pre- and post-solvent selective herbicidal and growth-regulating properties. In this formula, A represents one by halogen, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-haloalkoxy, C1-C4-haloalkylthio, C1-C4-haloalkylsulfinyl or C1-C4-haloalkylsulfonyl-substituted C1-C6-alkyl radical, or a C2-C6-alkenyl radical substituted by the radicals listed, E the methine group or nitrogen, X oxygen, sulfur, a sulfinyl or sulfonyl bridge, Z oxygen or sulfur, m the Number one or two, R1 hydrogen, halogen, C1-C5-alkyl, C2-C5-alkenyl or a radical -Y-R5, R2 hydrogen, halogen, C1-C5-alkyl, C2-C5-alkenyl C1-C4-haloalkyl , or a radical -Y-R5, -COOR6, -NC or -CO-NR7-R8, R³ hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, halogen , C1-C4-haloalkoxy or alkoxyalkyl with a maximum of 4 carbon atoms, R4 C1-C4-haloalkoxy or C1-C4-haloalkylthio, R5 and R6 each C1-C5alkyl, C3-C5-alkenyl or C2-C6-alkynyl, R7 and R8 independently from each other hydrogen, C1-C5-alkyl, C2-C5-alkenyl or C2-C6-alkynyl and Y oxygen, sulfur, a sulfinyl or sulfonyl bridge. where A can also stand for the unsubstituted C2-C6 alkenyl radical if X simultaneously denotes oxygen.

Description

Die vorliegende Erfindung betrifft neue, herbizid wirksame und pflanzenwuchsregulierende N-Phenylsulfonyl-N'-pyrimidinyl- und -triazinylharnstoffe, Verfahren zu ihrer Herstellung, sie als Wirkstoffe erthaltende Mittel, sowie deren Verwendung zum Bekämpfen von Unkräutern, vor allem selektiv in Nutzpflanzenkulturen oder zum Regulieren und Hemmen des Pflanzenwachstums:The present invention relates to new, herbicidally active and plant growth-regulating N-phenylsulfonyl-N'-pyrimidinyl- and -triazinylureas, processes for their preparation, agents containing them as active compounds, and their use for controlling weeds, especially selectively in crops or for regulating and inhibiting plant growth:

Die erfindungsgemässen N-Phenylsulfonyl-N'-pyrimidinyl- und -triazinylharnstoffe entsprechen der allgemeinen Formel I

Figure imgb0001
worin

  • A einen durch Halogen, C1-C4-Alkoxy, C1-C4 Alkylthio, C1-C4 Alkylsulfinyl, C1-C4-Alkylsulfonyl, C1-C4 Halogenalkoxy, C1-C4 Halogenalkylthio, C1-C4-Halogenalkylsulfinyl oder Cl-C4-Halogenalkylsulfonyl substituierten Cl-C6-Alkylrest oder einen durch die aufgezählten Reste substituierten C2-C6-Alkenylrest,
  • E die Methingruppe oder Stickstoff,
  • X Sauerstoff, Schwefel, eine Sulfinyl- oder Sulfonylbrücke,
  • Z Sauerstoff oder Schwefel,
  • m die Zahl eins oder zwei,
  • R1 Wasserstoff, Halogen, C1-C5-Alkyl, C2-C5-Alkenyl oder einen Rest -Y-R5,
  • R 2 Wasserstoff, Halogen, C1 C5-Alkyl, C2-C5-Alkenyl, C1-C4-Halogenalkyl, oder einen Rest -Y-R5, -COOR6, -NO2 oder -CO-NR7-R8,
  • R3 Wasserstoff, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Alkylthio, CI-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen oder Alkoxyalkyl mit CD höchstens 4 Kohlenstoffatomen,
  • R4 C1-C4-Halogenalkoxy oder C1-C4 Halogenalkylthio,
  • R 5 und R 6 je C1-C5-Alkyl, C2-C5-Alkenyl oder C2-C6-Alkinyl,
  • R7 und R8 unabhängig voneinander Wasserstoff, C1-C5-Alkyl, C2-C5-Alkenyl oder C2-C6-Alkinyl und
  • Y Sauerstoff, Schwefel, eine Sulfinyl- oder Sulfonylbrücke bedeuten, wobei A auch für den unsubstituierten C2-C6-Alkenylrest stehen kann, wenn gleichzeitig X Sauerstoff bedeutet, sowie den Salze dieser Verbindungen.
The N-phenylsulfonyl-N'-pyrimidinyl- and -triazinylureas according to the invention correspond to the general formula I.
Figure imgb0001
 wherein
  • A by halogen, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkylthio, C 1 -C 4 haloalkylsulfinyl or C 1 -C 4 haloalkylsulfonyl substituted C 1 -C 6 alkyl radicals or a C 2 -C 6 alkenyl radical substituted by the listed radicals,
  • E the methine group or nitrogen,
  • X oxygen, sulfur, a sulfinyl or sulfonyl bridge,
  • Z oxygen or sulfur,
  • m the number one or two,
  • R 1 is hydrogen, halogen, C 1 -C 5 alkyl, C 2 -C 5 alkenyl or a radical -YR 5 ,
  • R 2 is hydrogen, halogen, C 1 C 5 alkyl, C 2 -C 5 alkenyl, C 1 -C 4 haloalkyl, or a radical -YR 5 , -COOR 6 , -NO 2 or -CO-NR 7 - R 8 ,
  • R 3 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 -alkylthio, C I -C 4 haloalkyl, C 1 -C 4 haloalkoxy, halogen or alkoxyalkyl of at most CD 4 carbon atoms,
  • R 4 C 1 -C 4 haloalkoxy or C 1 -C 4 haloalkylthio,
  • R 5 and R 6 e j C 1 -C 5 alkyl, C 2 -C 5 alkenyl or C 2 -C 6 alkynyl,
  • R 7 and R 8 independently of one another hydrogen, C 1 -C 5 alkyl, C 2 -C 5 alkenyl or C 2 -C 6 alkynyl and
  • Y is oxygen, sulfur, a sulfinyl or sulfonyl bridge, where A can also represent the unsubstituted C 2 -C 6 alkenyl radical if X is oxygen at the same time, and the salts of these compounds.

Harnstoffverbindungen, Triazinverbindungen und Pyrimidinverbindungen mit herbizider Wirkung sind allgemein bekannt. Kürzlich wurden Arylsulfamoyl-heterocyclyl-aminocarbamoylverbindungen mit herbizider und pflanzenwuchsregulierender Wirkung, beispielsweise im holländischen - Patent 121 788, den europäischen Patentpublikationen Nr. 9419, 23422, dem US Patent Nr. 4 127 405, in der DT-OS 2 715 786 oder in der FR-PS 1 468 747 beschrieben.Urea compounds, triazine compounds and pyrimidine compounds with herbicidal activity are generally known. Arylsulfamoyl-heterocyclyl-aminocarbamoyl compounds with herbicidal and plant growth-regulating activity have recently been disclosed, for example in Dutch patent 121 788, European patent publications No. 9419, 23422, US patent No. 4 127 405, in DT-OS 2,715,786 or in FR-PS 1 468 747.

In den Definitionen ist unter Alkyl geradkettiges oder verzweigtes Alkyl zu verstehen; z.B.: Methyl, Aethyl, n-Propyl, i-Propyl, die vier isomeren Butyl, n-Amyl, i-Amyl, 2-Amyl, 3-Amyl, n-Hexyl oder i-Hexyl.In the definitions, alkyl is to be understood as straight-chain or branched alkyl; e.g .: methyl, ethyl, n-propyl, i-propyl, the four isomeric butyl, n-amyl, i-amyl, 2-amyl, 3-amyl, n-hexyl or i-hexyl.

Unter Alkoxy ist zu verstehen: Methoxy, Aethoxy, n-Propyloxy, i-Propyloxy und die vier isomeren Butyloxyreste, insbesondere aber Methoxy, Aethoxy oder i-Propoxy.Alkoxy is to be understood as: methoxy, ethoxy, n-propyloxy, i-propyloxy and the four isomeric butyloxy radicals, but especially methoxy, ethoxy or i-propoxy.

Beispiele für Alkylthio sind Methylthio, Aethylthio, n-Propylthio, i-Propylthio und n-Butylthio, insbesondere aber Methylthio und Aethylthio.Examples of alkylthio are methylthio, ethylthio, n-propylthio, i-propylthio and n-butylthio, but especially methylthio and ethylthio.

Beispiele für Alkenylreste sind Vinyl, Allyl, Isopropenyl, 1-Propenyl, 1-Butenyl, 2-Butenyl, 3-Butenyl, 1-Isobutenyl, 2-Isobutenyl, 1-Pentenyl, 2-Pentenyl, 3-Pentenyl und 4-Pentenyl, insbesondere aber Vinyl, Allyl und 4-Pentenyl.Examples of alkenyl radicals are vinyl, allyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-isobutenyl, 2-isobutenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl and 4-pentenyl, but especially vinyl, allyl and 4-pentenyl.

Beispiele für Alkylsulfinyl sind Methylsulfinyl, Aethylsulfinyl, n-Propylsulfinyl und n-Butylsulfinyl, insbesondere aber Methylsulfinyl und Aethylsulfinyl.Examples of alkylsulfinyl are methylsulfinyl, ethylsulfinyl, n-propylsulfinyl and n-butylsulfinyl, but especially methylsulfinyl and ethylsulfinyl.

Beispielefür Alkylsulfonyl sind Methylsulfonyl, Aethylsulfonyl, n-Propylsulfonyl und n-Butylsulfonyl, insbesondere aber Methylsulfonyl und Aethylsulfonyl.Examples of alkylsulfonyl are methylsulfonyl, ethylsulfonyl, n-propylsulfonyl and n-butylsulfonyl, but especially methylsulfonyl and ethylsulfonyl.

Unter Halogen in den Definitionen sowie in Halogenalkyl, -alkoxy, -alkylsulfinyl, -alkylsulfonyl und -alkylthio sind Fluor, Chlor und Brom, vorzugsweise jedoch Fluor und Chlor zu verstehen.Halogen in the definitions and in haloalkyl, alkoxy, alkylsulfinyl, alkylsulfonyl and alkylthio are to be understood as fluorine, chlorine and bromine, but preferably fluorine and chlorine.

Bevorzugte Halogenalkylreste, die auch Bestandteile grösserer Substituentengruppen sein können, wie z.B. eines Halogenalkoxy- oder Halogenalkylthiorestes, sind Difluormethyl, Trifluormethyl, Perfluoräthyl, 2,2,2-Trifluoräthyl, Chlorfluormethyl, Bromfluormethyl, 2-Chloräthyl, 1,1,2,2-Tetrafluoräthyl, 2-Fluoräthyl, 2,2,2-Trichloräthyl, Bromdifluormethyl, Chlordifluormethyl, 1,1,2-Trifluor-2-chloräthyl, 1,1,2-Trifluor-2-bromäthyl, 1,1,2,3,3,3-Hexafluorpropyl, insbesondere aber Difluormethyl, 2,2,2-Trifluoräthyl und Perfluoräthyl.Preferred haloalkyl radicals, which can also be constituents of larger substituent groups, such as e.g. of a haloalkoxy or haloalkylthio radical are difluoromethyl, trifluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, chlorofluoromethyl, bromofluoromethyl, 2-chloroethyl, 1,1,2,2-tetrafluoroethyl, 2-fluoroethyl, 2,2,2-trichloroethyl , Bromodifluoromethyl, chlorodifluoromethyl, 1,1,2-trifluoro-2-chloroethyl, 1,1,2-trifluoro-2-bromoethyl, 1,1,2,3,3,3-hexafluoropropyl, but especially difluoromethyl, 2.2 , 2-trifluoroethyl and perfluoroethyl.

Alkinylresten in den Definitionen der obigen Symbole entsprechen in der Regel Propargyl, 2-Butinyl, 3-Butinyl, sowie isomere Pentinyl-oder Hexinylreste, vorzugsweise ist der Alkinylrest jedoch durch Propargyl oder 2- oder 3-Butinyl verkörpert.Alkynyl radicals in the definitions of the above symbols generally correspond to propargyl, 2-butynyl, 3-butynyl, and isomeric pentynyl or hexynyl radicals, but the alkynyl radical is preferably embodied by propargyl or 2- or 3-butynyl.

Die Erfindung umfasst ebenfalls die Salze, die die Verbindungen der Formel I mit Aminen, Alkali- und Erdalkalimetallbasen oder quaternären Ammoniumbasen bilden können.The invention also encompasses the salts which the compounds of the formula I can form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.

Unter Alkali- und Erdalkalimetallhydroxiden als Salzbildner sind die Hydroxide von Lithium, Natrium, Kalium, Magnesium oder Calcium hervorzuheben, insbesondere aber die von Natrium oder Kalium.Among alkali and alkaline earth metal hydroxides as salt formers, the hydroxides of lithium, sodium, potassium, magnesium or calcium should be emphasized, but especially those of sodium or potassium.

Beispiele für zur Salzbildung geeignete Amine sind primäre, sekundäre und tertiäre aliphatische und aromatische Amine wie Methylamin, Aethylamin, Propylamin, i-Propylamin, die vier isomere Butylamine, Dimethylamin, Diäthylamin, Diäthanolamin, Dipropylamin, Diisopropylamin, Di-n-butylamin, Pyrrolidin, Piperidin, Morpholin, Trimethylamin, Triäthylamin, Tripropylamin, Chinuclidin, Pyridin, Chinolin und i-Chinolin, insbesondere aber Aethyl-, Propyl-, Diäthyl- oder Triäthylamin, vor allem aber iso-Propylamin und Diäthanolamin.Examples of amines suitable for salt formation are primary, secondary and tertiary aliphatic and aromatic amines such as methylamine, ethylamine, propylamine, i-propylamine, the four isomeric butylamines, dimethylamine, diethylamine, diethanolamine, dipropylamine, diisopropylamine, di-n-butylamine, pyrrolidine, Piperidine, morpholine, trimethylamine, triethylamine, tripropylamine, quinuclidine, pyridine, quinoline and i-quinoline, but especially ethyl-, propyl-, diethyl- or triethylamine, but especially isopropylamine and diethanolamine.

Beispiele für quaternäre Ammoniumbasen sind im allgemeinen die Kationen von Halogenammoniumsalzen, z.B. das Tetramethylammoniumkation, das Trimethylbenzylammoniumkation, das Triäthylbenzylammoniumkation, das Tetraäthylammoniumkation, das Trimethyläthylammoniumkation, aber auch das Ammoniumkation.Examples of quaternary ammonium bases are generally the cations of halogen ammonium salts, e.g. the tetramethylammonium cation, the trimethylbenzylammonium cation, the triethylbenzylammonium cation, the tetraethylammonium cation, the trimethylethylammonium cation, but also the ammonium cation.

Von den erfindungsgemässen Verbindungen der FormelIsind die Verbindungen bevorzugt, in denen entweder

  • a) X oder
  • b) Z Sauerstoff oder
  • c) m die Zahl eins bedeuten oder
  • d) die Reste R3 und R4 zusammen nicht mehr als 4 Kohlenstoffatome enthalten.
Of the compounds of the formula I according to the invention, preference is given to the compounds in which either
  • a) X or
  • b) Z oxygen or
  • c) m is the number one or
  • d) the radicals R 3 and R 4 together contain no more than 4 carbon atoms.

Durch Kombination der bevorzugten Merkmale ergibt sich folgende weiter bevorzugten Gruppe von Verbindungen der Formel I, in denen .Combining the preferred features results in the following further preferred group of compounds of the formula I in which.

X und Z Sauerstoff und m die Zahl eins bedeuten und der Rest -X-A die ortho-Position' zur Sulfonylgruppe besetzt.X and Z are oxygen and m is the number one and the radical -X-A occupies the ortho position 'to the sulfonyl group.

Innerhalb dieser Gruppe sind weiterhin die Verbindungen bevorzugt, in denen'die Reste R3 und R4 zusammen nicht mehr als 4 Kohlenstoffatome enthalten.Within this group, the compounds in which the radicals R 3 and R 4 together contain no more than 4 carbon atoms are also preferred.

Besonders bevorzugt sind innerhalb dieser Untergruppe die Verbindungen, in denen R4 für Halogenäthoxy und Halogenmethoxy steht. Hiervon sind wiederum die Verbindungen bevorzugt, in denen R4 den 2,2,2-Trifluoräthoxyrest oder den Difluormethoxyrest bedeutet.Particularly preferred within this subgroup are the compounds in which R 4 represents halogen ethoxy and halogen methoxy. Of these, the compounds in which R 4 is the 2,2,2-trifluoroethoxy radical or the difluoromethoxy radical are again preferred.

Als bevorzugte Einzelverbindungen sind.zu nennen:

  • N-(2-Difluormethoxyphenyl-sülfonyl)-N'-[4-methoxy-6-.(2,2,2-trifluor- äthoxy)-1,3,5-triazin-2-yl]-harnstoff, N-[2-(2-Chloräthoxy)-phenylsulfonyl]-N'-[4-methoxy-6-(2,2,2-trifluoräthoxy)-1,3,5-triazin-2-yl]-harnstoff, N-(2-Trifluormethoxyphenyl-sulfonyl)-N'-(4-difluormethoxy-6-methyl-pyrimidin-2-yl)-harnstoff und N-(2-Difluormethoxyphenyl- sulfonyl)-N'-(4-difluormethoxy-6-methyl-pyrimidin-2-yl)-harnstoff.
The following are preferred individual connections:
  • N- (2-difluoromethoxyphenylsulfonyl) -N '- [4-methoxy-6 -. (2,2,2-trifluoro-ethoxy) -1,3,5-triazin-2-yl] urea, N- [2- (2-chloroethoxy) phenylsulfonyl] -N '- [4-methoxy-6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] urea, N- ( 2-trifluoromethoxyphenylsulfonyl) -N '- (4-difluoromethoxy-6-methyl-pyrimidin-2-yl) urea and N- (2-difluoromethoxyphenylsulfonyl) -N' - (4-difluoromethoxy-6-methyl- pyrimidin-2-yl) urea.

Die Herstellung der Verbindungen der Formel I erfolgt in einem inerten, organischen Lösungsmittel.The compounds of the formula I are prepared in an inert, organic solvent.

Nach einem ersten Verfahren werden die Verbindungen der Formel I erhalten, indem man ein Phenylsulfonamid der Formel II

Figure imgb0002
worin A, R1, R2, X und m die unter Formel I gegebenen Bedeutung haben, in Gegenwart einer Base mit einem N-Pyrimidinyl- oder -Triazinylcarbamat der Formel III
Figure imgb0003
worin E, R3, R4 und Z die unter Formel I gegebene Bedeutung haben, und R11 für Wasserstoff, Halogen, Nitro oder C1-C3-Alkyl steht, umsetzt.According to a first process, the compounds of formula I are obtained by using a phenylsulfonamide of formula II
Figure imgb0002
 wherein A, R 1 , R 2 , X and m have the meaning given under formula I, in the presence of a base with an N-pyrimidinyl or triazinyl carbamate of the formula III
Figure imgb0003
 wherein E, R 3 , R 4 and Z have the meaning given under formula I, and R 11 represents hydrogen, halogen, nitro or C 1 -C 3 alkyl.

Nach einem zweiten Verfahren gelangt man zu Verbindungen der Formel I, indem man ein Phenylsulfonylisocyanat oder -isothiocyanat der Formel IV

Figure imgb0004
worin A, R1, R2, m, X und Z die unter Formel I gegebene Bedeutung haben, gegebenenfalls in Gegenwart einer Base, mit einem Amin der Formel V
Figure imgb0005
worin E, R3 und R4 die unter Formel I gegebene Bedeutung haben, umsetzt.A second process gives compounds of the formula I by using a phenylsulfonyl isocyanate or isothiocyanate of the formula IV
Figure imgb0004
 wherein A, R 1 , R 2 , m, X and Z have the meaning given under formula I, optionally in the presence of a base, with an amine of formula V.
Figure imgb0005
 in which E, R 3 and R 4 have the meaning given under formula I.

Nach einem weiteren Verfahren werden die Verbindungen der Formel I hergestellt, indem man ein Sulfonamid der oben angegebenen FormeIII gegebenenfalls in Gegenwart einer Base mit einem Isocyanat oder Isothiocyanat der Formel VI

Figure imgb0006
worin E, R3, R4 und Z die unter Formel I gegebene Bedeutung haben, umsetzt.According to a further process, the compounds of the formula I are prepared by, if appropriate in the presence of a base, a sulfonamide of the above formula III with an isocyanate or isothiocyanate of the formula VI
Figure imgb0006
 in which E, R 3 , R 4 and Z have the meaning given under formula I.

Schliesslich kann man die Verbindungen der Formel I auch erhalten, indem man ein N-Phenylsulfonylcarbamat der Formel VII

Figure imgb0007
worin A, R1, R2, m und X die unter Formel I gegebene Bedeutung haben und R11 für asserstoff, Halogen, Nitro oder C1-C3-Alkyl steht, mit einem Amin der oben angegebenen Formel V umsetzt.Finally, the compounds of the formula I can also be obtained by using an N-phenylsulfonylcarbamate of the formula VII
Figure imgb0007
 in which A, R 1 , R 2 , m and X have the meaning given under formula I and R 11 represents aeric, halogen, nitro or C 1 -C 3 -alkyl, reacted with an amine of formula V given above.

Die erhaltenen Harnstoffe der Formel I können gewünschtenfalls mittels Aminen, Alkalimetall- oder Erdalkalimetallhydroxiden oder quaternären Ammoniumbasen in Additionssalze übergeführt werden. Dieses geschieht beispielsweise durch Umsetzen mit der äquimolaren Menge Base und Verdampfen des Lösungsmittels.If desired, the ureas of the formula I obtained can be converted into addition salts using amines, alkali metal or alkaline earth metal hydroxides or quaternary ammonium bases. This is done, for example, by reacting with the equimolar amount of base and evaporating the solvent.

Die Ausgangsstoffe der Formel II, IV, VII und ortho-substituierte Hydroxyphenyl- resp. substituierte ortho-Hydroxyphenylsulfonamide der Formel VIII,

Figure imgb0008
worin R und R2 die unter Formel 1 angegebene Bedeutung haben und X' für Sauerstoff oder Schwefel steht, als Ausgangsprodukte bestimmter Sulfonamid-Vertreter der Formel II, sind aus der europäischen Patentanmeldung 44 807 bekannt.The starting materials of formula II, IV, VII and ortho-substituted hydroxyphenyl, respectively. substituted ortho-hydroxyphenylsulfonamides of the formula VIII,
Figure imgb0008
 wherein R and R 2 have the meaning given under formula 1 and X 'represents oxygen or sulfur, as starting products of certain sulfonamide representatives of the formula II, are known from European patent application 44 807.

Die Ausgangsmaterialien der Formeln III, V und VI sind zum Teil bekannt. Neue Verbindungen der Formeln III und VI können nach bekannten Methoden aus entsprechenden Verbindungen der Formel V erhalten werden.Some of the starting materials of the formulas III, V and VI are known. New compounds of the formulas III and VI can be obtained by known methods from corresponding compounds of the formula V.

Neue Fluoralkoxy-aminopyrimidine und -triazine der Formel V und ihre Herstellung sowie die Herstellung entsprechender Verbindungen der Formeln III und VI daraus werden in der schweizerischen Patentanmeldung 3527/82-8 beschrieben.New fluoroalkoxy aminopyrimidines and triazines of the formula V and their preparation and the preparation of corresponding compounds of the formulas III and VI are described in Swiss patent application 3527 / 82-8.

Die Umsetzungen zu Verbindungen der Formel I werden vorteilhafterweise in aprotischen, inerten, organischen Lösungsmitteln vorgenommen wie Methylenchlorid, Tetrahydrofuran, Acetonitril, Dioxan, Toluol. Als Basen können sowohl organische Basen wie Amine, wie Triäthylamin, Chinuclidin, Chinolin, Pyridin etc. als auch anorganische Basen wie Hydride wie Natrium- oder Calciumhydrid, Hydroxide wie Natrium- und Kaliumhydroxid, Carbonate wie Natrium- und Kaliumcarbonat oder Hydrogencarbonate wie Kalium- und Natriumhydrogencarbonat verwendet werden.The reactions to compounds of formula I are advantageously carried out in aprotic, inert, organic solvents such as methylene chloride, tetrahydrofuran, acetonitrile, dioxane, toluene. As bases both organic bases such as amines such as triethylamine, quinuclidine, quinoline, pyridine etc. as well as inorganic bases such as hydrides such as sodium or calcium hydride, hydroxides such as sodium and potassium hydroxide, carbonates such as sodium and potassium carbonate or hydrogen carbonates such as potassium and Sodium bicarbonate can be used.

Die Reaktionstemperaturen liegen vorzugsweise zwischen -20° und +120°C. Die Umsetzungen verlaufen im allgemeinen leicht exotherm und können bei Raumtemperatur durchgeführt werden. Zwecks Abkürzung der Reaktionszeit oder auch zum Einleiten der Umsetzung wird zweckdienlich für kurze Zeit bis zum Siedepunkt des Reaktionsgemisches aufgewärmt.The reaction temperatures are preferably between -20 ° and + 120 ° C. The reactions are generally slightly exothermic and can be carried out at room temperature. In order to shorten the reaction time or to initiate the reaction, the mixture is expediently warmed up briefly to the boiling point of the reaction mixture.

Die Endprodukte können durch Einengen und/oder Verdampfen des Lösungsmittels isoliert und durch Umkristallisieren oder Zerreiben des festen Rückstandes in Lösungsmitteln in denen sie sich nicht gut lösen, wie Aether, aromatischen Kohlenwasserstoffen oder chlorierten Kohlenwasserstoffen gereinigt werden.The end products can be isolated by concentrating and / or evaporating the solvent and can be purified by recrystallizing or triturating the solid residue in solvents in which they do not dissolve well, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.

Die Wirkstoffe der Formel I sind stabile Verbindungen. Ihre Handhabung bedarf keine vorsorglicher Massnahmen.The active ingredients of formula I are stable compounds. Their handling does not require any precautionary measures.

Bei geringeren Aufwandmengen zeichnen sich die Verbindungen der Formel I durch gute selektiy-wuchshemmende und selektiv-herbizide Eigenschaften aus, die sie ausgezeichnet zum Einsatz in Kulturen von Nutzpflanzen, insbesondere in Getreide, Baumwolle, Soja, Mais und Reis, befähigen. Es werden dabei teilweise auch Unkräuter geschädigt, welchen bisher nur mit Totalherbiziden beizukommen war.At lower application rates, the compounds of the formula I are notable for good selective growth-inhibiting and selective herbicidal properties which make them excellent for use in crops of useful plants, in particular in cereals, cotton, soybeans, corn and rice. Weeds are sometimes damaged, which previously could only be dealt with with total herbicides.

Die Wirkungsart dieser Wirkstoffe ist unüblich. Viele sind translozierbar, d.h. sie werden von der Pflanze aufgenommen und an andere Stellen transportiert, wo sie dann zur Wirkung kommen. So gelingt es beispielsweise, durch Oberflächenbehandlung perenierende Unkräuter bis in die Wurzeln zu schädigen. Die neuen Verbindungen der Formel I wirken bereits bei - im Vergleich zu anderen Herbiziden und Wuchsregulatoren - sehr geringen Aufwandmengen.The mode of action of these active substances is unusual. Many are translocable, i.e. they are taken up by the plant and transported to other places, where they then come into effect. For example, surface weeding can damage perennial weeds down to the roots. The new compounds of formula I already have a very low application rate compared to other herbicides and growth regulators.

Die Verbindungen der Formel I haben ausserdem starke pflanzenwuchsregulierende Eigenschaften, die sich in einer Ertragssteigerung von Kulturpflanzen oder Erntegut auswirken kann. Viele Verbindungen der Formel I zeigen darüberhinaus eine konzentrationsabhängige pflanzenwuchshemmende Wirkung. Es werden sowohl Monokotyledonen als auch Dikotyledonen in ihrem Wachstum beeinträchtigt.The compounds of the formula I also have strong plant growth-regulating properties which can have an effect on increasing the yield of crop plants or crops. Many compounds of formula I also show a concentration-dependent plant growth-inhibiting effect. Both monocots and dicots are impaired in their growth.

So können z.B. die in der Landwirtschaft in tropischen Gegenden häufig als "cover crops" (Bodenbedecker) angepflanzten Leguminosen durch die Verbindungen der Formel I in ihrem Wachstum selektiv gehemmt werden, so dass zwar die Bodenerosion zwischen den Kulturpflanzen verhindert wird, die "cover crops" jedoch nicht zur Konkurrenz für die Kultur werden können.For example, the legumes which are often cultivated in agriculture in tropical regions as "cover crops" are selectively inhibited in their growth by the compounds of the formula I, so that soil erosion between the crop plants is prevented, but the "cover crops" are not Can become competition for culture.

Eine Hemmung des vegetativen Wachstums erlaubt bei vielen Kulturpflanzen eine dichtere Anpflanzung der Kultur, so dass ein Mehrertrag, bezogen auf die Bodenfläche, erzielt werden kann.An inhibition of vegetative growth allows a denser cultivation of the crop in many crop plants, so that an additional yield, based on the soil area, can be achieved.

Ein weiterer Mechanismus der Ertragssteigerung mit Wachstumshemmern beruht darauf, dass die Nährstoffe in stärkerem Masse der Blüten- und Fruchtbildung zugute kommen, während das vegetative Wachstum eingeschränkt wird.Another mechanism of increasing yield with growth inhibitors is based on the fact that the nutrients benefit the bloom and fruit formation to a greater extent, while vegetative growth is restricted.

Weiter eignen sich die Verbindungen der Formel I um das Keimen von eingelagerten Kartoffeln zu verhindern._Bei Kartoffeln entwickeln sich bei der Einlagerung über den Winter häufig Keime, die Schrumpfen, Gewichtsverlust und Faulen zur Folge haben.The compounds of the formula I are also suitable for preventing the germination of stored potatoes. When potatoes are stored over the winter, germs often develop which result in shrinkage, weight loss and rotting.

Bei grösseren Aufwandmengen werden alle getesteten Pflanzen in ihrer Entwicklung so geschädigt, dass sie absterben.At higher application rates, all tested plants are damaged in their development so that they die.

Die Erfindung betrifft auch herbizide und pflanzenwachstumsregulierende Mittel, welche einen neuen Wirkstoff der Formel I enthalten, sowie Verfahren zur pre- und post-emergenten Unkrautbekämpfung, zur Hemmung des Pflanzenwuchses von monokotylen und dikotylen Pflanzen, insbesondere Gräsern, tropischen Bodenbedeckern und Tabakgeiztrieben .und zur Regulierung des Pflanzenwachstums insbesondere von Leguminosen. Die Verbindungen der Formel I werden in unveränderter Form oder vorzugsweise als Mittel zusammen mit den in der Formulierungstechnik üblichen Hilfsmitteln eingesetzt und werden daher z.B. zu Emulsionskonzentraten, direkt versprühbaren oder verdünnbaren Lösungen, verdünnten Emulsionen, Spritzpulvern, löslichen Pulvern, Stäubemitteln, Granulaten, auch Verkapselungen in z.B. polymeren Stoffen in bekannter Weise verarbeitet. Die Anwendungsverfahren wie Versprühen, Vernebeln, Verstäuben, Verstreuen oder Giessen werden gleich wie die Art der Mittel den angestrebten Zielen und den gegebenen Verhältnissen entsprechend gewählt.The invention also relates to herbicidal and plant growth regulating compositions which contain a novel compound of formula I, and to methods for pre- and post-emergent weed control, for inhibiting the growth of monocots and dicots, especially grasses, tro p regard crops and tobacco plant suckers .and to regulate plant growth, especially of legumes. The compounds of the formula I are used in unchanged form or, preferably, as agents together with the auxiliaries customary in formulation technology and are therefore used, for example, to form emulsion concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in eg polymeric materials processed in a known manner. The application methods, such as spraying, atomizing, dusting, scattering or pouring, are selected in the same way as the type of agent, in accordance with the desired objectives and the given conditions.

Die Formulierungen, d.h. die den Wirkstoff der Formel I und gegebenenfalls einen festen oder flüssigen Zusatzstoff enthaltenden Mittel, Zubereitungen oder Zusammensetzungen werden in bekannter Weise hergestellt, z.B. durch inniges Vermischen und/oder Vermahlen der Wirkstoffe mit Streckmitteln, wie z.B. mit Lösungsmitteln, festen Trägerstoffen, und gegebenenfalls oberflächenaktiven Verbindungen (Tensiden). Als Lösungsmittel können in Frage kommen: Aromatische Kohlenwasserstoffe, bevorzugt die Fraktionen C8 bis C12, wie z.B. Xylolgemische oder substituierte Naphthaline, Phthalsäureester wie Dibutyl- oder Dioctylphthalat, aliphatische Kohlenwasserstoffe wie Cyclohexan oder Paraffine, Alkohole und Glykole sowie deren Aether und Ester, wie Aethanol, Aethylenglykol, Aethylenglykolmonomethyl- oder-äthyläther, Ketone wie Cyclohexanon, stark polare Lösungsmittel wie N-Methyl-2-pyrrolidon, Dimethylsulfoxid oder Dimethylformamid, sowie gegebenenfalls epoxidierte Pflanzenöle, wie epoxidiertes Kokosnussöl oder Sojaöl; oder Wasser.The formulations, ie the agents, preparations or compositions comprising the active ingredient of the formula I and, if appropriate, a solid or liquid additive, are prepared in a known manner, for example by intimately mixing and / or grinding the active ingredients with extenders, for example with solvents, solid carriers, and optionally surface-active compounds (surfactants). Possible solvents are: Aromatic hydrocarbons, preferably fractions C 8 to C 12 , such as xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as Ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.

Als feste Trägerstoffe, z.B. für Stäubemittel und dispergierbare Pulver, werden in der Regel natürliche Gesteinsmehle verwendet, wie Calcit, Talkum, Kaolin, Montmorillonit oder Attapulgit. Zur Verbesserung der 'physikalischen Eigenschaften können auch hochdisperse Kieselsäure oder hochdisperse saugfähige Polymerisate zugesetzt werden. Als gekörnte, adsorptive Granulatträger kommen poröse Typen wie z.B. Bimsstein, Ziegelbruch, Sepiolit oder Bentonit, als nicht sorptive Trägermaterialien z.B. Calcit oder Sand in Frage. Darüberhinaus kann eine Vielzahl von vorgänulierten Materialien anorganischer oder organischer Natur wie insbesondere Dolomit oder zerkleinerte Pflanzenrückstände verwendet werden.Natural rock flours, such as calcite, talc, kaolin, montmorillonite or attapulgite, are generally used as solid carriers, for example for dusts and dispersible powders. To improve the 'physical properties and highly dispersed silicic acid or highly dispersed absorbent polymers may be added. Porous types such as pumice, broken brick, sepiolite or bentonite can be used as granular, adsorptive granulate carriers, and non-sorptive carrier materials, such as calcite or sand. In addition, a large number of preanulated materials of inorganic or organic nature, such as in particular dolomite or comminuted plant residues, can be used.

Als oberflächenaktive Verbindungen kommen je nach der Art des zu formulierenden Wirkstoffes der Formel I nichtionogene, kation- und/oder anionaktive Tenside mit guten Emulgier-, Dispergier- und Netzeigenschaften in Betracht. Unter Tensiden sind auch Tensidgemische zu verstehen.Depending on the nature of the active ingredient of the formula I to be formulated, suitable surface-active compounds are nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties. Surfactants are also to be understood as mixtures of surfactants.

Geeignete anionische Tenside können sowohl sog. wasserlösliche Seifen als auch wasserlösliche synthetische oberflächenaktive Verbindungen sein.Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.

Als Seifen seien die Alkali-, Erdalkali- oder gegebenenfalls substituierte Amnioniumsalze von höheren Fettsäuren (C10-C22), wie z.B. die Na- oder K-Salze der Oel- oder Stearinsäure, oder von natürlichen Fettsäuregemischen, die z.B. aus Kokosnuss- oder Talgöl gewonnen werden können, genannt. Ferner sind auch die Fettsäure-methyl-taurinsalze zu erwähnen.The soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (C 10 -C 22 ), such as, for example Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained, for example, from coconut or tallow oil. The fatty acid methyl taurine salts should also be mentioned.

Häufiger werden jedoch sogenannte synthetische Tenside verwendet, insbesondere Fettsulfonate, Fettsulfate, sulfonierte Benzimidazolderivate oder Alkylarylsulfonate.However, so-called synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

Die Fettsulfonate oder -sulfate liegen in der Regel als Alkali-, Erdalkali- oder gegebenenfalls substituierte Ammoniumsalze vor und weisen einen Alkylrest mit 8 bis 22 C-Atomen auf, wobei Alkyl auch den Alkylteil von Acylresten einschliesst, z.B. das Na- oder Ca-Salz der Ligninsulfonsäure, des Dodecylschcaefelsäureesters oder eines aus natürlichen Fettsäuren hergestellten Fettalkoholsulfatgemisches. Hierher gehören auch die Salze der Schwefelsäureester und Sulfonsäuren von Fettalkohol-Aethylenoxid-Addukten. Die sulfonierten Benzimidazolderivate enthalten vorzugsweise 2-Sulfonsäuregruppen und einen Fettsäurerest mit 8-22 C-Atomen. Alkylarylsulfonate sind z.B. die Na-, Ca- oder Triäthanolaminsalze der Dodecylbenzolsulfonsäure, der Dibutylnaphthalinsulfonsäure oder eines Naphthalinsulfonsäure-Formaldehydkondensationsproduktes.The fatty sulfonates or sulfates are usually present as alkali, alkaline earth or optionally substituted ammonium salts and have an alkyl radical with 8 to 22 carbon atoms, alkyl also including the alkyl part of acyl radicals, e.g. the Na or Ca salt of lignin sulfonic acid, dodecyl sulfate or a fatty alcohol sulfate mixture made from natural fatty acids. This subheading also includes the salts of sulfuric acid esters and sulfonic acids from fatty alcohol / ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2-sulfonic acid groups and a fatty acid residue with 8-22 carbon atoms. Alkylarylsulfonates are e.g. the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or a naphthalenesulfonic acid-formaldehyde condensation product.

Ferner kommen auch entsprechende Phosphate wie z.B. Salze des Phosphorsäureesters eines p-Nonylphenol-(4-14)-Aethylenoxid-Adduktes in Frage.Corresponding phosphates such as e.g. Salts of the phosphoric acid ester of a p-nonylphenol (4-14) ethylene oxide adduct in question.

Als nicht ionische Tenside kommen in erster Linie Polyglykolätherderivate von aliphatischen oder cycloaliphatischen Alkoholen, gesättigten oder ungesättigten Fettsäuren und Alkylphenolen-in Frage, die 3 bis 30 Glykoläthergruppen und 8 bis 20 Kohlenstoffatome im (aliphatischen) Kohlenwasserstoffrest und 6 bis 18 Kohlenstoffatome in Alkylrest der Alkylphenole enthalten können.Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols can.

Weitere geeignete nichtionische Tenside sind die wasserlöslichen, 20 bis 250 Aethylenglykoläthcrgruppen und 10 bis 100 Propylenglykoläthergruppen enthaltenden Polyäthylenoxidaddukte an Polypropylenglykol, Aethylendiaminopolypropylenglykol und Alkylpolypropylenglykol mit 1 bis 10 Kohlenstoffatomen in der Alkylkette. Die genannten Verbindungen enthalten üblicherweise pro Propylenglykol-Einheit 1 bis 5 Aethylenglykoleinheiten.Other suitable nonionic surfactants are the water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Als Beispiele nichtionischer Tenside seien Nonylphenolpolyäthoxy äthanole, Ricinusölpolyglykoläther, Polypropylen-Polyäthylenoxidaddukte, Tributylphenoxypolyäthanol, Polyäthylenglykol und Octylphenoxypolyäthoxyäthanol erwähnt.Examples of nonionic surfactants are nonylphenol polyethoxy ethanol, castor oil polyglycol ether, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Ferner kommen auch Fettsäureester von Polyoxyäthylensorbitan wie das Polyoxyäthylensorbitaa-trioleat in Betracht.Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbita trioleate, are also suitable.

Bei den kationischen Tensiden handelt es sich vor allem um quaternäre Ammoniumsalze, welche als N-Substituenten mindestens einen Alkylrest mit 8 bis 22 C-Atomen enthalten und als weitere Substituenten niedrige, gegebenenfalls halogenierte Alkyl-, Benzyl-oder niedrige Hydroxyalkylreste aufweisen. Die Salze liegen vorzugsweise als Halogenide, Methylsulfate oder Aethylsulfate vor, z.B. das Stearyltrimethylammoniurmchlorid oder das Benzyldi(2-chloräthyl)-äthylammoniumbromid.The cationic surfactants are primarily quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 carbon atoms as N substituents and have lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl radicals as further substituents. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. the stearyltrimethylammonium chloride or the benzyldi (2-chloroethyl) ethylammonium bromide.

Die in der Formulierungstechnik gebräuchlichen Tenside sind u.a. in folgenden Publikationen beschrieben:

  • "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood, New Jersey, 1979.
  • Sisley and Wood, "Encyclopedia of Surface Active Agents".
  • Chemical Publishing Co., Inc. New York, 1964.
The surfactants commonly used in formulation technology are described in the following publications:
  • "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood, New Jersey, 1979.
  • Sisley and Wood, "Encyclopedia of Surface Active Agents".
  • Chemical Publishing Co., Inc. New York, 1964.

Die pestiziden Zubereitungen enthalten in der Regel 0,1 bis 95%, insbesondere 0,1 bis 80%, Wirkstoff der Formel I, 1 bis 99,9% eines festen oder flüssigen Zusatzstoffes und 0 bis 25%, insbesondere 0,1 bis 25% eines Tensides.The pesticidal preparations generally contain 0.1 to 95%, in particular 0.1 to 80%, active ingredient of the formula I, 1 to 99.9% of one solid or liquid additive and 0 to 25%, in particular 0.1 to 25% of a surfactant.

Insbesondere setzen sich bevorzugte Formulierungen folgendermassen zusammen: (% = Gewichtsprozetic)In particular, preferred formulations are composed as follows: (% = weight percentage)

Emulgierbare KonzentrateEmulsifiable concentrates

Figure imgb0009
Figure imgb0009

StäubeDusts

Figure imgb0010
Figure imgb0010

Suspension-KonzentrateSuspension concentrates

Figure imgb0011
Figure imgb0011

Benetzbare PulverWettable powder

Figure imgb0012
Figure imgb0012

GranulateGranules

Figure imgb0013
Während als Handelsware eher konzentrierte Mittel bevorzugt werden, verwendet der Endverbraucher in der Regel verdünnte Mittel. Die Anwendungsformen können bis hinab zu 0,001% an Wirkstoff verdünnt werden. Die Aufwandmengen betragen in der Regel 0,01 bis 10 kg AS/ha, vorzugsweise 0,025 bis 5 kg AS/ha.
Figure imgb0013
 While concentrated agents are preferred as a commodity, the end user generally uses diluted agents. The use forms can be diluted down to 0.001% of active ingredient. The application rates are generally 0.01 to 10 kg ai / ha, preferably 0.025 to 5 kg ai / ha.

Die Mittel können auch weitere Zusätze wie Stabilisatoren, Entschäumer, Viskositätsregulatoren, Bindemittel, Haftmittel sowie Dünger oder andere Wirkstoffe zur Erzielung spezieller Effekte enthalten.The agents can also contain other additives such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers or other active ingredients to achieve special effects.

In den folgenden Beispielen sind die Temperaturen in Celsiusgraden °C, die Drücke in Millibar mb angegeben.In the following examples the temperatures are in degrees Celsius, the pressures in millibars mb.

Herstellungsbeispiele:Manufacturing examples: Beispiel 1: N-(2-Difluormethoxyphenyl-sulfonyl)-N'-[4-methoxy-6-(2,2,2-trifluoräthoxy)-1,3,5-triazin-2-yl]-harnstoff.Example 1: N- (2-difluoromethoxyphenylsulfonyl) -N '- [4-methoxy-6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] urea.

  • a) Zur Suspension von 80,3 g 2-Amino-4-chlor-6-methoxy-1,3,5-triazin in 400 ml absolutem Dioxan lässt man in 10 Minuten 124,6 g 2-Difluormethoxyphenyl-sulfonylisocyanat in 100 ml Dioxan zutropfen. Die Reaktionsmischung wird für 3 Stunden auf 90-100° erwärmt. Durch Abkühlen und Einengen der Reaktionslösung erhält man 180 g N-(2-Difluormethoxyphenyl-sulfonyl)-N'-(4-chlor-6-methoxy-l,3,5-triazin-2-yl)-harnstoff, Smp. 167-168°.a) 124.6 g of 2-difluoromethoxyphenylsulfonyl isocyanate in 100 ml are left over 10 minutes to suspend 80.3 g of 2-amino-4-chloro-6-methoxy-1,3,5-triazine in 400 ml of absolute dioxane Drop of dioxane. The reaction mixture is heated to 90-100 ° for 3 hours. Cooling and concentrating the reaction solution gives 180 g of N- (2-difluoromethoxyphenylsulfonyl) -N '- (4-chloro-6-methoxy-l, 3,5-triazin-2-yl) urea, mp. 167 -168 °.
  • b) Eine Mischung aus 8,2 g N-(2-Difluormethoxyphenyl-sulfonyl)-N'-(4-chlor-6-methoxy-1,3,5-triazin-2-yl)-harnstoff, 60 ml Dioxan, 20 ml 2,2,2-Trifluoräthanol und 5,5 g Kaliumcarbonat wird für 12 Stunden bei 55-60° gerührt, dann in 300 ml Wasser aufgenommen und über Aktivkohle filtriert. Nach dem Ansäuern des Gemisches mit 2 n Salzsäure, fällt das Produkt aus und wird durch Filtration abgetrennt. Ausbeute: 7,7 g N-(2-Difluormethoxyphenyl-sulfonyl)-N'-[4-methoxy-6-(2,2,2-trifluoräthoxy)=1,3,5-triazin-2-yl]-harnstoff, Smp. 155-157°.b) a mixture of 8.2 g of N- (2-difluoromethoxyphenylsulfonyl) -N '- (4-chloro-6-methoxy-1,3,5-triazin-2-yl) urea, 60 ml of dioxane, 20 ml of 2,2,2-trifluoroethanol and 5.5 g of potassium carbonate are stirred at 55-60 ° for 12 hours, then taken up in 300 ml of water and filtered through activated carbon. After acidifying the mixture with 2N hydrochloric acid, the product precipitates and is separated off by filtration. Yield: 7.7 g of N- (2-difluoromethoxyphenylsulfonyl) -N '- [4-methoxy-6- (2,2,2-trifluoroethoxy) = 1,3,5-triazin-2-yl] urea , Mp 155-157 °.
Beispiel 2: N-(2-Difluormethoxyphenyl-sulfonyl)-N'-(4-difluormethoxy-6-methyl-pyrimidin-2-yl)-harnstoff.Example 2: N- (2-difluoromethoxyphenylsulfonyl) -N '- (4-difluoromethoxy-6-methyl-pyrimidin-2-yl) urea.

  • a) In eine Lösung von 62,5 g 2-Amino-4-hydroxy-6-methyl-pyrimidin in 500 ml Wasser, 100 ml 40%iger Natriumhydroxidlösung und 100 ml Dioxan wird über einen Zeitrum von 12 Stunden bei einer Temperatur von 70-75°C gasförmiges Difluorchlormethan eingeleitet. Während-dieses Zeitraumes fügt man, jeweils im Abstand von 1 Stunde, in gleichen Portionen insgesamt 160 g festes Natriumhydroxid zu. Durch Abtrennen der organischen Phase, Einengen auf ca. 1/10 des Volumens, Eingiessen des Rückstandes in Wasser und Abtrennen des ausgefallenen Feststoffes erhält man 39,9 g 2-Amino-4-difluormethoxy-6-methyl-pyrimidin, Smp. 136-137°C.a) In a solution of 62.5 g of 2-amino-4-hydroxy-6-methyl-pyrimidine in 500 ml of water, 100 ml of 40% sodium hydroxide solution and 100 ml of dioxane is over a period of 12 hours at a temperature of 70 -75 ° C gaseous difluorochloromethane initiated. During this period, a total of 160 g of solid sodium hydroxide is added in equal portions at intervals of 1 hour. By separating the organic phase, concentrating to about 1/10 of the volume, pouring the residue into water and separating the precipitated solid, 39.9 g of 2-amino-4-difluoromethoxy-6-methyl-pyrimidine, mp. 136- 137 ° C.
  • b) Eine Mischung aus 2,5 g 2-Difluormethoxyphenyl-sulfonylisocyanat, 1,75 g 2-Amino-4-difluormethoxy-6-methyl-pyrimidin und 30 ml absolutem Dioxan wird . für 2 Stunden bei einer Temperatur von 70-75°C gerührt. Durch Eindampfen der Lösung und Kristallisation des Rückstandes aus Aether erhält man 4,0 g N-(2-Difluormethoxyphenyl-sulfonyl)-N'-(4- difluormethoxy-6-methyl-pyrimidin-2-yl)-harnstoff, Smp. 163-164°C.b) A mixture of 2.5 g of 2-difluoromethoxyphenyl sulfonyl isocyanate, 1.75 g of 2-amino-4-difluoromethoxy-6-methyl-pyrimidine and 30 ml of absolute dioxane. stirred for 2 hours at a temperature of 70-75 ° C. Evaporation of the solution and crystallization of the residue from ether gives 4.0 g of N- (2-difluoromethoxyphenylsulfonyl) -N '- (4-difluoromethoxy-6-methyl-pyrimidin-2-yl) urea, mp. 163 -164 ° C.
Beispiel 3: N-[2-(2-Aethoxy-äthoxy)-phenyl-sulfonyl]-N'-(4-difluor- methoxy-6-methyl-pyrimidin-2-yl)-harnstoff.Example 3: N- [2- (2-ethoxyethoxy) phenylsulfonyl] -N '- (4-difluoro-methoxy-6-methyl-pyrimidin-2-yl) urea.

  • a) Einer Lösung von 9,0 g (0,05 Mol) 2-Amino-4-difluormethoxy-6-methyl- pyrimidin in 30 ml absolutem Tetrahydrofuran werden nacheinander 3,9 g (0,025 Mol) Chlorameisensäure-phenylester und 0,05 g 4-Dimethylamino-pyridin zugesetzt. Nach Rühren der Lösung bei 20-25°C für 24 Stunden wird das Reaktionsgemisch mit 250 ml Aethylacetat verdünnt und der ausgefallene Niederschlag abgetrennt. Man erhält so 3,1 g 2-Amino-4-difluormethoxy-6-methyl-pyrimidin-hydrochlorid, Smp. 204-205°C (Zers.). Das Filtrat wird zur Entfernung des restlichen Ausgangsstoffes über eine Säule mit Ionenaustauscher I® MERCK) eluiert, über Natriumsulfat getrocknet und eingedampft. Man erhält so in Form eines viskosen Oeles als Rohprodukt 4,0 g 2-Phenoxycarbonyl- amino-4-difluormethoxy-6-methyl-pyrimidin , das nach der Kristallisation bei 56-58° C schmilzt. 1H-NMR (CDCl3) . δ - 2,5 (s,CH3, 6,45 (s,lH), 7,0-7,5 (5H), 7,56 (t,J=70 Hz, CHF2) und 9,0 (NH) ppm.a) A solution of 9.0 g (0.05 mol) of 2-amino-4-difluoromethoxy-6-methyl-pyrimidine in 30 ml of absolute tetrahydrofuran are successively 3.9 g (0.025 mol) of phenyl chloroformate and 0.05 g 4-Dimethylamino-pyridine added. After the solution has been stirred at 20-25 ° C. for 24 hours, the reaction mixture is diluted with 250 ml of ethyl acetate and the precipitate which has separated out is separated off. This gives 3.1 g of 2-amino-4-difluoromethoxy-6-methyl-pyrimidine hydrochloride, mp. 204-205 ° C (dec.). To remove the remaining starting material, the filtrate is eluted on a column with ion exchanger I® MERCK), dried over sodium sulfate and evaporated. This gives 4.0 g of 2-phenoxycarbonyl crude product in the form of a viscous oil. amino-4-difluoromethoxy-6-methyl-pyrimidine, which melts at 56-58 ° C after crystallization. 1 H NMR (CDCl 3 ). δ - 2.5 (s, CH 3 , 6.45 (s, lH), 7.0-7.5 (5H), 7.56 (t, J = 70 Hz, CHF 2 ) and 9.0 ( NH) ppm.
  • b) Eine Lösung von 3,5 g (0,012 Mol) 2-Phenoxycarbonylamino-4-difluor- methoxy-6-methyl-pyrimidin-Rohprodukt und 2,9 g (0,012 Mol) 2-(2-Aethoxy-äthoxy)-benzolsulfonamid in 100 ml absolutem Acetonitril wird mit 1,8 g (0,012 Mol) 1,5-Diazabicyclc(5,4,0)undec-5-en versetzt, für 1 Stunde bei 20-25°C gerührt, dann mit 500 ml Wasser verdünnt und mit Salzsäure angesäuert. Das abgeschiedene Oel wird mit 200 ml Aethylacetat aufgenommen über Natriumsulfat getrocknet und eingedampft. Durch Kristallisieren des öligen Rückstandes aus Diäthyläther und Aceton erhält man als farbloses Kristallisat N-[2-(2-Aethoxy-äthoxy)-phenyl-sulfonyl]-N'-(4-difluormethoxy-6-methyl-pyrimidin-2-yl)-harn-. stoff, Smp. 90-95°C (Zers.), Ausbeute 2,7 g.b) A solution of 3.5 g (0.012 mol) of 2-phenoxycarbonylamino-4-difluoromethoxy-6-methyl-pyrimidine crude product and 2.9 g (0.012 mol) of 2- (2-ethoxy-ethoxy) -benzenesulfonamide in 100 ml of absolute acetonitrile, 1.8 g (0.012 mol) of 1,5-diazabicyclc (5,4,0) undec-5-ene are added, the mixture is stirred at 20-25 ° C. for 1 hour, then with 500 ml of water diluted and acidified with hydrochloric acid. The separated oil is taken up in 200 ml of ethyl acetate, dried over sodium sulfate and evaporated. Crystallization of the oily residue from diethyl ether and acetone gives N- [2- (2-ethoxyethoxy) phenylsulfonyl] -N '- (4-difluoromethoxy-6-methylpyrimidin-2-yl) as a colorless crystallizate. -urine-. fabric, mp 90-95 ° C (dec.), yield 2.7 g.
Beispiel 4: 2-Amino-4-difluormethylthio-6-methoxy-1,3,5-triazin.Example 4: 2-Amino-4-difluoromethylthio-6-methoxy-1,3,5-triazine.

In eine Suspension von 5,0 g 2-Amino-4-mercapto-6-methoxy-1,3,5-triazin und 4,8 g Kaliumcarbonat in 100 ml Dimethylformamid werden während eines Zeitraums von 90 Minuten bei einer Temperatur von 70-75°C 10,0 g gasförmiges Difluorchlormethan eingeleitet. Durch Eindampfen des Reaktionsgemisches, Verrühren des Rückstandes mit Wasser und Abtrennen des festen Niederschlages erhält man 1,6 g 2-Amino-4-Difluormethylthio-6-methoxy-1,3,5-triazin, Smp. 146-150°C.In a suspension of 5.0 g of 2-amino-4-mercapto-6-methoxy-1,3,5-triazine and 4.8 g of potassium carbonate in 100 ml of dimethylformamide are placed over a period of 90 minutes at a temperature of 70- 75 ° C 10.0 g of gaseous difluorochloromethane are introduced. Evaporation of the reaction mixture, stirring of the residue with water and removal of the solid precipitate gives 1.6 g of 2-amino-4-difluoromethylthio-6-methoxy-1,3,5-triazine, mp. 146-150 ° C.

Beispiel 5: 2-Amino-4-chlor-6-difluormethoxy-pyrimidinExample 5: 2-Amino-4-chloro-6-difluoromethoxypyrimidine

Eine Suspension von 16,4 g 2-Amino-4,6-dichlor-pyrimidin in 100 ml 40%iger Natriumhydroxidlösung wird für 1 Stunde bei einer Temperatur von 95-100°C gerührt. Nach Zusatz von 200 ml Dioxan werden bei einer Temperatur von 70-75°C innerhalb von 1 Stunde 20 g gasförmiges Difluorchlormethan eingeleitet. Durch Abtrennen der organischen Phase, Einengen auf ca. 1/5 des Volumens, Eingiessen in Wasser und Abtrennen des festen Niederschlages erhält man 6 g 2-eimino-4-chlor-6-difluor- methoxy-pyrimidin, Smp. 118-119°C.A suspension of 16.4 g of 2-amino-4,6-dichloropyrimidine in 100 ml of 40% sodium hydroxide solution is stirred at a temperature of 95-100 ° C. for 1 hour. After adding 200 ml of dioxane, 20 g of gaseous difluorochloromethane are introduced at a temperature of 70-75 ° C. within 1 hour. By separating the organic phase, Concentration to about 1/5 of the volume, pouring into water and separating off the solid precipitate gives 6 g of 2-eimino-4-chloro-6-difluoromethoxy-pyrimidine, mp. 118-119 ° C.

Beispiel 6: 2-Amino-4-difluormethoxy-6-methoxy-pyrimidinExample 6: 2-Amino-4-difluoromethoxy-6-methoxypyrimidine

19,2 g 2-Amino-4,6-dimethoxy-pyrimidin-hydrochlorid werden während 2 Stunden auf 150°C erhitzt, wobei sich unter Abspaltung von Methylchlorid 2-Amino-4-hydroxy-6-methoxy-pyrimidin bildet. Nach Zusatz von 80 ml 40%iger Natriumhydroxidlösung und 100 ml Dioxan werden bei 70-75° während 3/4 Stunden 22 g Difluorchlormethan eingeleitet. Durch Abtrennen der org. Phase, Einengen auf ca. 1/5 des Volumens, Eingiessen in Wasser und Abtrennen des festen Niederschlages erhält man 2,4 g 2-Amino-4-difluormethoxy-6-methoxy-pyrimidin, Smp. 106-107°C.19.2 g of 2-amino-4,6-dimethoxy-pyrimidine hydrochloride are heated at 150 ° C. for 2 hours, 2-amino-4-hydroxy-6-methoxy-pyrimidine being formed with the elimination of methyl chloride. After adding 80 ml of 40% sodium hydroxide solution and 100 ml of dioxane, 22 g of difluorochloromethane are introduced at 3/4 to 70 ° -75 ° for 3/4 hours. By separating the org. Phase, concentration to about 1/5 of the volume, pouring into water and separating off the solid precipitate gives 2.4 g of 2-amino-4-difluoromethoxy-6-methoxy-pyrimidine, mp. 106-107 ° C.

Beispiel 7: 2-Amino-4-methyl-6-[1,1,2-trifluor-2-chlor-äthoxy]- pyrimidinExample 7: 2-Amino-4-methyl-6- [1,1,2-trifluoro-2-chloroethoxy] pyrimidine

25 g 2-Amino-4-hydroxy-6-methyl-pyrimidin, 25,6g.Chlortrifluoräthylen, 13,8 g Kaliumhydroxyd und 200 ml Dimethylformamid werden zusammen während 8 Stunden bei 60° im Autoklaven gerührt. Durch Verdünnen mit Wasser, Extrahieren mit Essigester und Eindampfen erhält man ein dunkles Oel. Nach der Zugabe von wenig Methylenchlorid und Abtrennen des gebildeten kristallinen Niederschlages erhält man 8,7 g 2-Amino-4-methyl-6-(1,1,2-trifluor-2-chlor-äthoxy)-pyrimidin, Smp. 73-74°C.25 g of 2-amino-4-hydroxy-6-methyl-pyrimidine, 25.6 g of chlorotrifluoroethylene, 13.8 g of potassium hydroxide and 200 ml of dimethylformamide are stirred together in an autoclave at 60 ° for 8 hours. Dilution with water, extraction with ethyl acetate and evaporation give a dark oil. After adding a little methylene chloride and separating off the crystalline precipitate formed, 8.7 g of 2-amino-4-methyl-6- (1,1,2-trifluoro-2-chloroethoxy) pyrimidine, mp. 73- 74 ° C.

In analoger Weise erhält man die in den anschliessenden Tabellen aufgelisteten Endprodukte.The end products listed in the tables below are obtained in an analogous manner.

Figure imgb0014
Figure imgb0014
Figure imgb0015
Figure imgb0015
Figure imgb0016
Figure imgb0016
Figure imgb0017
Figure imgb0017
Figure imgb0018
Figure imgb0018
Figure imgb0019
Figure imgb0019
Figure imgb0020
Figure imgb0020
Figure imgb0021
Figure imgb0021
Figure imgb0022
Figure imgb0022
Figure imgb0023
Figure imgb0023
Figure imgb0024
Figure imgb0024
Figure imgb0025
Figure imgb0025
Figure imgb0026
Figure imgb0026
Figure imgb0027
Figure imgb0027
Figure imgb0028
Figure imgb0028
Figure imgb0029
Figure imgb0029
Figure imgb0030
Figure imgb0030
Figure imgb0031
Figure imgb0031
Figure imgb0032
Figure imgb0032
Figure imgb0033
Figure imgb0033
Figure imgb0034
Figure imgb0034
Figure imgb0035
Figure imgb0035
Figure imgb0036
Figure imgb0036
Figure imgb0037
Figure imgb0037
Figure imgb0038
Figure imgb0038
Figure imgb0039
Figure imgb0039
Figure imgb0040
Figure imgb0040
Figure imgb0041
Figure imgb0041
Figure imgb0042
Figure imgb0042
Figure imgb0043
Figure imgb0043
Figure imgb0044
Figure imgb0044
Figure imgb0045
Figure imgb0045
Figure imgb0046
Figure imgb0046
Figure imgb0047
Figure imgb0047
Figure imgb0048
Figure imgb0048
Figure imgb0049
Figure imgb0049
Figure imgb0050
Figure imgb0050

FormulierungsbeispieleFormulation examples -Beispiel 8: Formulierungsbeispiele für Wirkstoffe der Formel IExample 8: Formulation examples for active ingredients of the formula I. (% = Gewichtsprozent)(% = Weight percent)

Figure imgb0051
Der Wirkstoff wird mit den Zusatzstoffen gut vermischt und in einer geeigneten Mühle gut vermahlen. Man erhält Spritzpulver, die sich mit Wasser zu Suspensionen jeder gewünschten Konzentration verdünnen lassen.
Figure imgb0052
Figure imgb0051
 The active ingredient is mixed well with the additives and ground well in a suitable mill. Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.
Figure imgb0052

Aus diesem Konzentrat können durch Verdünnen mit Wasser Emulsionen jeder gewünschten Konzentration hergestellt werden.

Figure imgb0053
Emulsions of any desired concentration can be prepared from this concentrate by dilution with water.
Figure imgb0053

Man erhält anwendungsfertige Stäubemittel, indem der Wirkstoff mit dem Träger vermischt und auf einer geeigneten Mühle vermahlen wird.

Figure imgb0054
Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding it in a suitable mill.
Figure imgb0054

Der Wirkstoff wird mit den Zusatzstoffen vermischt, vermahlen und mit Wasser angefeuchtet. Dieses Gemisch wird extrudiert und anschliessend im Luftstrom getrocknet.

Figure imgb0055
The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in an air stream.
Figure imgb0055

Der fein gemahlene Wirkstoff wird in einem Mischer auf das mit Polyäthylenglykol angefeuchtete Kaolin gleichmässig aufgetragen. Auf diese Weise erhält man staubfreie Umhüllungs-Granulate.

Figure imgb0056
Figure imgb0057
 The finely ground active ingredient is evenly applied in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.
Figure imgb0056
Figure imgb0057

Der fein gemahlene Wirkstoff wird mit den Zusatzstoffen innig vermischt. Man erhält so ein Suspensions-Konzentrat, aus welchem durch Verdünnen mit Wasser Suspensionen jeder gewünschten Konzentration hergestellt werden können.

Figure imgb0058
The finely ground active ingredient is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
Figure imgb0058

Biologische Beispiele Beispiel 9: Nachweis der Herbizidwirkung vor dem Auflaufen der PflanzenBiological Examples Example 9: Detection of the herbicidal activity before the plants emerge

Im Gewächshaus werden Pflanzensamen in Blumentöpfe von 12-15 cm Durchmesser gesät. Unmittelbar danach wird die Erdoberfläche mit einer wässrigen Dispersion oder Lösung der Wirkstoffe behandelt. Es werden Konzentrationen von 4 kg Wirkstoffmengen pro Hektar angewendet. Die Töpfe werden dann im Gewächshaus bei einer Temperatur von 22-25°C und 50-70 % relativer Luftfeuchtigkeit gehalten. Nach 3 Wochen wird der Versuch ausgewertet und die Wirkung auf die Versuchspflanzen nach dem folgenden Massstab bewertet:

  • 1: Pflanze nicht gekeimt oder total abgestorben
  • 2-3: sehr starke Wirkung
  • 4-6: mittlere Wirkung
  • 7-8: schwache Wirkung
  • 9: keine Wirkung (wie unbehandelte Kontrolle).
In the greenhouse, plant seeds are sown in flower pots with a diameter of 12-15 cm. Immediately afterwards, the surface of the earth is treated with an aqueous dispersion or solution of the active ingredients. Concentrations of 4 kg of active ingredient per hectare are used. The pots are then kept in the greenhouse at a temperature of 22-25 ° C and 50-70% relative humidity. After 3 weeks, the test is evaluated and the effect on the test plants is assessed on the following scale:
  • 1: Plant not germinated or totally dead
  • 2-3: very strong effect
  • 4-6: medium effect
  • 7-8: weak effect
  • 9: no effect (like untreated control).

Pre-emergente WirkungPre-emergent effect

Aufwandmenge: 4 kg Wirksubstanz/Hektar

Figure imgb0059
Application rate: 4 kg of active substance / hectare
Figure imgb0059

Beispiel 10: Nachweis der Selektivität bei VorauflaufanwendungExample 10: Proof of selectivity in pre-emergence applications

In der gleichen Versuchsanordnung wie im Beispiel 9 werden eine grössere Anzahl von Pflanzensamen mit verschiedenen Aufwandmengen an Wirksubstanz behandelt. Die Auswertung erfolgt nach dem gleichen Massstab.In the same experimental set-up as in Example 9, a large number of plant seeds are treated with different amounts of active substance. The evaluation is carried out on the same scale.

pre-emergente Wirkung:pre-emergent effect:

Figure imgb0060
Figure imgb0060

Beispiel 11: Nachweis der Herbizidwirkung nach dem Auflaufen derExample 11: Detection of the herbicidal action after emergence of the Pflanzen (Kontaktwirkung)Plants (contact effect)

Eine Anzahl Unkräuter und Kulturpflanzen, sowohl monokotyle wie dikotyle, werden nach dem Auflaufen, im 4- bis 6-Blattstadium mit einer wässrigen Wirkstoffdispersion in Dosierungen von 4 kg AS/ha gespritzt und dann bei 24° bis 26°C und 45-60% relativer Luftfeuchtigkeit gehalten. 15 Tage nach der Behandlung wird der Versuch ausgewertet und nach dem gleichen Massstab wie im pre-emergenten Versuch bewertet.A number of weeds and crops, both monocotyledonous and dicotyledonous, are sprayed after emergence in the 4- to 6-leaf stage with an aqueous active ingredient dispersion in doses of 4 kg AS / ha and then at 24 ° to 26 ° C. and 45-60% relative humidity kept. 15 days after the treatment, the test is evaluated and evaluated on the same scale as in the pre-emergent test.

Post-emergente wirkungPost-emergent effect Aufwandmenge: 4 kg wirksubstanz/HektarApplication rate: 4 kg of active substance / hectare

Figure imgb0061
Figure imgb0061

Beispiel 12; Nachweis der Selektivität bei NachauflaufanwendungExample 12; Proof of selectivity in post-emergence applications

In der gleichen Versuchsanordnung wie im Beispiel 11 werden eine grössere Anzahl von Pflanzen mit verschiedenen Aufwandmengen an Wirksubstanz behandelt. Die Auswertung erfolgt nach dem in Beispiel 9 angegebenen Massstab.In the same experimental setup as in Example 11, a large number of plants are treated with different amounts of active substance. The evaluation is carried out on the scale given in Example 9.

post-emergente Wirkungpost-emergent effect

Figure imgb0062
Beispiel 13: Nachweis der Keimhemmung an Lagerkartoffeln.
Figure imgb0062
 Example 13: Detection of the inhibition of germs on stored potatoes.

Eine Anzahl im Handel erhältliche Kartoffeln der Sorte "Urgenta" ohne Keime werden gewaschen und abgetrocknet. Danach werden die Kartoffeln für jeweils eine Minute in Wirkstoffemulsionen verschiedener Konzentration getaucht, in Kunststoffschalen auf Filterpapier ausgelegt und bei Temperaturen von 14° und 21°C im Dunkeln bei 50 % relativer Luftfeuchtigkeit gehalten. Die Auswertung erfolgte 34 Tage nach der Applikation. Gleichzeitig wird der Gewichtsverlust der Knollen und das Gewicht der Keime im Vergleich zur unbehandelten Kontrolle ermittelt. Die erfindungsgemässen Verbindungen zeigten in diesem Versuch eine vollständige Verhinderung der Keimbildung. Gleichzeitig betrug der Gewichtsverlust der Kartoffeln weniger als 10 % des Gewichtsverlustes der Kontrollkartoffeln.A number of commercially available "Urgenta" potatoes without germs are washed and dried. The potatoes are then immersed in active ingredient emulsions of different concentrations for one minute each, placed in plastic trays on filter paper and kept at temperatures of 14 ° and 21 ° C. in the dark at 50% relative atmospheric humidity. The evaluation was carried out 34 days after the application. At the same time, the weight loss of the tubers and the weight of the germs are determined in comparison to the untreated control. In this experiment, the compounds according to the invention showed complete prevention of nucleation. At the same time, the weight loss of the potatoes was less than 10% of the weight loss of the control potatoes.

Beispiel 14: Nachweis der Wuchshemmung bei tropischen Bodendeckern-Leguminosen (cover crops)Example 14: Detection of growth inhibition in tropical ground cover legumes (cover crops)

In Kunststoffschalen mit Erde-Torf-Sand-Gemisch (1:1:1) werden Testpflanzen der Sorte Psophocarpus palustris und Centrosema pubescens aus Stecklingen angezogen. Nach dem Anwurzeln werden die Pflänzchen in 9 cm-Töpfe umgetopft und nach Bedarf gewässert. Die weitere Anzucht der Pflanzen findet im Gewächshaus bei einer Tagestemperatur von 27°C und einer Nachttemperatur von 21°C, bei einer mittleren Lichtdauer von 14 h (6000 Lux) und einer Luftfeuchtigkeit von 70% statt. Die Testpflanzen werden auf eine Höhe von ca. 15 cm zurückgeschnitten und 7 Tage nach dem Zurückschneiden mit einer Spritzbrühe des Wirkstoffs (umgerechnet 0,3 bzw. 3 kg Aktivsubstanz pro Hektar) besprüht. 4 Wochen nach Applikation wird das Wachstum der behandelten Pflanzen im Vergleich zu gestutzten, aber unbehandelten Kontrollpflanzen verglichen. In diesem Versuch zeigen die mit den Wirkstoffen der Formel I behandelten Pflanzen eine deutliche Reduktion des Neuzuwachses (weniger als 20% des Neuzuwachses bei unbehandelten Kontrollpflanzen) ohne dass dabei die Versuchspflanzen geschädigt werden.Test plants of the cultivars Psophocarpus palustris and Centrosema pubescens from cuttings are grown in plastic trays with a soil-peat-sand mixture (1: 1: 1). After rooting, the plantlets are repotted in 9 cm pots and watered as needed. The plants are further grown in the greenhouse at a day temperature of 27 ° C. and a night temperature of 21 ° C., with an average light duration of 14 h (6000 lux) and a humidity of 70%. The test plants are cut back to a height of approx. 15 cm and sprayed 7 days after cutting back with a spray mixture of the active ingredient (equivalent to 0.3 or 3 kg of active ingredient per hectare). 4 weeks after application, the growth of the treated plants is compared to trimmed but untreated control plants. In this test, the plants treated with the active compounds of the formula I showed a significant reduction in new growth (less than 20% of the new growth in untreated control plants) without the test plants being damaged in the process.

Beispiel 15: Nachweis der pre-emergenten Selektivität in Soja-KulturenExample 15: Detection of pre-emergent selectivity in soybean crops

In Kunststoffbehältern mit 30 1 Inhalt (60x30x25 cm) werden in sandig-lehmiger Ackererde die Versuchspflanzen ausgesät, mit einer 1-2 cm dicken Erdeschicht abgedeckt und mit Wasser angegossen. Nach einem Tag wird der Wirkstoff in Form einer wässrigen Spritzbrühe in einer Menge entsprechend 500 1/ha in Konzentrationen entsprechend 60 g/ha und 30 g/ha appliziert. Anschliessend werden die Behälter im Gewächshaus bei Temperaturen von 20-25°C gehalten und bei Bedarf gegossen. Nach 33 Tagen wird der Versuch ausgewertet und nach dem gleichen Massstab wie im Beispiel 9 bonitiert.The test plants are sown in sandy-loamy soil in plastic containers with 30 1 content (60x30x25 cm), covered with a 1-2 cm thick layer of soil and watered. After one day, the active ingredient is applied in the form of an aqueous spray mixture in an amount corresponding to 500 l / ha in concentrations corresponding to 60 g / ha and 30 g / ha. The containers are then kept in the greenhouse at temperatures of 20-25 ° C and poured if necessary. After 33 days, the test is evaluated and scored on the same scale as in Example 9.

Pre-emergente Wirkung in Soja-KulturenPre-emergent effects in soybean crops

Wirkstoff Nr. 31

Figure imgb0063
Active substance no.31
Figure imgb0063

Beispiel 16: Wuchsregulierung an SojabohnenExample 16: Growth regulation on soybeans

In Kunststoffbehältern mit einem Erde-Torf-Sandgemisch im Verhältnis 6:3:1 werden Sojabohnen der Sorte "Hark" angesät und in eine Klimakammer gegeben. Durch optimale Temperaturwahl, Beleuchtung, Düngerzugabe und Bewässerung entwickeln sich die Pflanzen nach ca. 5 Wochen bis zum 5-6 Trifolia-Blattstadium. Zu diesem Zeitpunkt werden die Pflanzen mit der wässrigen Brühe eines Wirkstoffes der Formel I bis zur guten Benetzung besprüht. Die Wirkstoffkonzentration beträgt bis zu 100 g AS/ha. Die Auswertung erfolgt ca. 5 Wochen nach der Applikation des Wirkstoffs. Im Vergleich zu unbehandelten Kontrollpflanzen bewirken die erfindungsgemässen Wirkstoffe der Formel I eine merkliche Erhöhung der Anzahl und des Gewichts der Schoten am Haupttrieb."Hark" soybeans are sown in plastic containers with a 6: 3: 1 soil-peat-sand mixture and placed in a climatic chamber. Through optimal temperature selection, lighting, adding fertilizer and irrigation, the plants develop after about 5 weeks until the 5-6 trifolia leaf stage. At this point, the plants are sprayed with the aqueous broth of an active ingredient of the formula I until thoroughly wetted. The active ingredient concentration is up to 100 g ai / ha. The evaluation takes place about 5 weeks after application of the active ingredient. In comparison to untreated control plants, the active compounds of the formula I according to the invention bring about a noticeable increase in the number and weight of the pods on the main shoot.

Wuchsregulierende Wirkung in Soja-KulturenGrowth regulating effect in soybean crops

Wirkstoff Nr. 31Active substance no.31

Figure imgb0064
Figure imgb0064

Claims (31)

1. Ein herbizides und den Pflanzenwuchs hemmendes Mittel, dadurch gekennzeichnet, dass es neben Träger- und/oder anderen Zuschlagstoffen als Wirkstoff mindestens einen N-Phenylsulfonyl-N'-triazinyl- oder -pyrimidinyl-harnstoff der Formel I
Figure imgb0072
oder ein Salz davon enthält, worin A einen durch Halogen, C1-C4-Alkoxy, C1-C4-Alkylthio, C1-C4 Alkylsulfinyl, C1-C4-Alkylsulfonyl, C1-C4-Halogenalkoxy, C1-C4-Halogen- alkylthio, C1-C4-Halogenalkylsulfinyl oder C1-C4-Halogenalkylsulfonyl substituierten C1-C6-Alkylrest oder einen durch.die aufgezählten Reste substituierten C2-C6-Alkenylrest, E die Methingruppe oder Stickstoff, X Sauerstoff, Schwefel, eine Sulfinyl- oder Sulfonylbrücke, Z Sauerstoff oder Schwefel, m die Zahl eins oder zwei, R1 Wasserstoff, Halogen, C1-C5-Alkyl, C2-C5-Alkenyl oder einen Rest -Y-R5' R2 Wasserstoff, Halogen, C1-C5-Alkyl, C2-C5-Alkenyl, C1-C4-Halogenalkyl, oder einen Rest -Y-R5, -COOR6, -TO2 Qder -CO-NR7-R8, R3 Wasserstoff, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Alkylthio, C1-C4-Halogenalkyl, Halogen, CI-C4-Halogenalkoxy oder Alkoxyalkyl mit höchstens 4 Kohlenstoffatomen, R 4 C1-C4-Halogenalkoxy oder C1-C4-Halogenalkylthio, R5 und R6 je C1-C5-Alkyl, C2-C5-Alkenyl oder C2-C6-Alkinyl, R7 und R8 unabhängig voneinander Wasserstoff, C1-C5-Alkyl, C2-C5-Alkenyl oder C2-C6-Alkinyl und Y Sauerstoff, Schwefel, eine Sulfinyl- oder Sulfonylbrücke bedeuten, wobei A auch für den unsubstituierten C2-C6-Alkenylrest stehen kann, wenn gleichzeitig X Sauerstoff bedeutet. 1. A herbicidal and plant growth-inhibiting agent, characterized in that it contains at least one N-phenylsulfonyl-N'-triazinyl- or -pyrimidinyl-urea of the formula I in addition to carriers and / or other additives
Figure imgb0072
 or contains a salt thereof, wherein A by halogen, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 -haloalkoxy, C 1 -C 4 - Haloalkylthio, C 1 -C 4 haloalkylsulfinyl or C 1 -C 4 haloalkylsulfonyl substituted C 1 -C 6 alkyl radical or a C 2 -C 6 alkenyl radical substituted by the enumerated radicals, E the methine group or nitrogen, X oxygen, sulfur, a sulfinyl or sulfonyl bridge, Z oxygen or sulfur, m the number one or two, R 1 is hydrogen, halogen, C 1 -C 5 alkyl, C 2 -C 5 alkenyl or a radical -YR 5 ' R 2 is hydrogen, halogen, C 1 -C 5 alkyl, C 2 -C 5 alkenyl, C 1 -C 4 haloalkyl, or a radical -YR 5 , -COOR 6 , -TO 2 Qder -CO-NR 7 -R8, R 3 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkyl, halogen, C I -C 4 haloalkoxy or alkoxyalkyl with at most 4 Carbon atoms, R 4 C 1 -C 4 haloalkoxy or C 1 -C 4 haloalkylthio, R 5 and R 6 are each C 1 -C 5 alkyl, C 2 -C 5 alkenyl or C 2 -C 6 alkynyl, R 7 and R 8 independently of one another hydrogen, C 1 -C 5 alkyl, C 2 -C 5 alkenyl or C 2 -C 6 alkynyl and Y is oxygen, sulfur, a sulfinyl or sulfonyl bridge, where A can also stand for the unsubstituted C 2 -C 6 alkenyl radical if X is also oxygen. 2. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass A einen durch Halogen, C1-C4-Alkoxy, C1-C4-Alkylthio, C1-C4-Alkylsulfinyl, C1-C4-Alkylsulfonyl, C1-C4-Halogenalkoxy, C1-C4-Halogen- alkylthio, C1-C4-Halogenalkylsulfinyl oder C1-C4-Halogenalkylsulfonyl substituierten C1-C6-Alkylrest oder einen durch die aufgezählten Reste substituierten C2-C6-Alkenylrest, E die Methingruppe oder Stickstoff, X Sauerstoff, Schwefel, eine Sulfinyl- oder Sulfonylbrücke, Z Sauerstoff oder Schwefel, m die Zahl eins oder zwei, R1 Wasserstoff, Halogen, C1-C5-Alkyl, C2-C5-Alkenyl oder einen Rest -Y-R5, R2 Wasserstoff, Halogen, C1-C5-Alkyl, C2-C5-Alkenyl, C1-C4-Halogenalkyl, oder einen Rest -Y-R5, -COOR6, -NOZ oder -CO-NR7-R8, R3 Wasserstoff, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Alkylthio, C1-C4-Halogenalkyl, Halogen, oder Alkoxyalkyl mit höchstens 4 Kohlenstoffatomen, R4 C1-C4-Halogenalkoxy , R5 und R 6 je C1-C5-Alkyl, C2-C5-Alkenyl oder C2-C6-Alkinyl, R7 und R8 unabhängig voneinander Wasserstoff, C1-C5-Alkyl, C2-C5-Alkenyl oder C2-C6-Alkinyl und Y Sauerstoff, Schwefel, eine Sulfinyl- oder Sulfonylbrücke bedeuten, wobei A auch für den unsubstituierten C2-C6-Alkenylrest stehen kanny wenn gleichzeitig X Sauerstoff bedeutet. 2. Composition according to claim 1, characterized in that A is a halogen, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkoxy, C 1 -C 4 Halogen alkylthio, C 1 -C 4 haloalkylsulfinyl or C 1 -C 4 haloalkylsulfonyl substituted C 1 -C 6 alkyl radical or a C 2 -C 6 alkenyl radical substituted by the listed radicals, E the methine group or nitrogen, X oxygen, sulfur, a sulfinyl or sulfonyl bridge, Z oxygen or sulfur, m the number one or two, R1 is hydrogen, halogen, C 1 -C 5 alkyl, C 2 -C 5 alkenyl or a radical -YR 5 , R 2 is hydrogen, halogen, C 1 -C 5 alkyl, C 2 -C 5 alkenyl, C 1 -C 4 haloalkyl, or a radical -YR 5 , -COOR 6 , -NO Z or -CO-NR 7 -R 8 , R 3 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkyl, halogen, or alkoxyalkyl with at most 4 carbon atoms, R 4 C 1 -C 4 haloalkoxy, R 5 and R 6 are each C 1 -C 5 alkyl, C 2 -C 5 alkenyl or C 2 -C 6 alkynyl, R7 and R 8 independently of one another hydrogen, C 1 -C 5 alkyl, C 2 -C 5 alkenyl or C 2 -C 6 alkynyl and Y is oxygen, sulfur, a sulfinyl or sulfonyl bridge, where A can also stand for the unsubstituted C 2 -C 6 alkenyl radical if X simultaneously denotes oxygen. 3. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass Z Sauerstoff bedeutet.3. Composition according to claim 1, characterized in that Z is oxygen. 4. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass X Sauerstoff bedeutet.4. Composition according to claim 1, characterized in that X is oxygen. 5. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass die Reste R3 und R4 zusammen nicht mehr als 4 Kohlenstoffatome enthalten.5. Composition according to claim 1, characterized in that the radicals R 3 and R 4 together contain no more than 4 carbon atoms. 6. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass m die Zähl eins bedeutet.6. Means according to claim 1, characterized in that m is the count one. 7. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass X und Z Sauerstoff und m die Zahl eins bedeuten und der Rest -X-A in der 2-Position zur Sulfonylgruppe steht.7. Composition according to claim 1, characterized in that X and Z are oxygen and m is the number one and the radical -X-A is in the 2-position to the sulfonyl group. 8. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass die Reste R3 und R4 zusammen nicht mehr als 4 Kohlenstoffatome enthalten.8. Composition according to claim 1, characterized in that the radicals R 3 and R 4 together contain no more than 4 carbon atoms. 9. Mittel gemäss Anspruch 8, dadurch gekennzeichnet, dass R4 für Halogenäthoxy steht.9. Composition according to claim 8, characterized in that R 4 represents halogen ethoxy. 10. Mittel gemäss Anspruch 8, dadurch gekennzeichnet, dass R4 für Halogenmethoxy steht.10. Composition according to claim 8, characterized in that R 4 is halogen methoxy. 11. Mittel gemäss Anspruch 9, dadurch gekennzeichnet, dass R4 den 2,2,2~Trifluoräthoxyrest bedeutet.11. Composition according to claim 9, characterized in that R 4 is the 2,2,2 ~ trifluoroethoxy radical. 12. Mittel gemäss Anspruch 10, dadurch gekennzeichnet, dass R4 den Difluormethoxyrest bedeutet.12. Composition according to claim 10, characterized in that R 4 is the difluoromethoxy radical. 13. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es als-.Wirkstoff N-(2-Difluormethoxyphenyl-sulfonyl)-N'-[4-methoxy-6-(2,2,2-trifluoräthoxy)-1,3,5-triazin-2-yl]-harnstoff enthält.13. Composition according to claim 1, characterized in that it is the. -Active substance N- (2-difluoromethoxyphenylsulfonyl) -N '- [4-methoxy-6- (2,2,2-trifluoroethoxy) -1,3, Contains 5-triazin-2-yl] urea. 14. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es als Wirkstoff N-(2-Difluormethoxyphenyl-sulfonyl)-N'-(4-difluormethoxy-6-methyl-pyrimidin-2-yl)-harnstoff enthält.14. Composition according to claim 1, characterized in that it contains N- (2-difluoromethoxyphenyl-sulfonyl) -N '- (4-difluoromethoxy-6-methyl-pyrimidin-2-yl) urea as active ingredient. 15. Verfahren zur Herstellung der Verbindungen der Formel I, Anspruch 1, dadurch gekennzeichnet, dass man a) ein Phenylsulfonamid der Formel II
Figure imgb0073
worin A, R1, R2, X und m die unter Formel I gegebene Bedeutung haben, in Gegenwart einer Base mit einem N-Pyrimidinyl- oder -Triazinylcarbamat der Formel
Figure imgb0074
worin E, R3, R4 und Z die unter Formel I gegebene Bedeutung haben und R11 für Wasserstoff, Halogen, Nitro oder C1-C3-Alkyl steht, umsetzt oder b) ein Phenylsulfonylisocyanat oder -isothiocyanat der Formel IV
Figure imgb0075
worin A, R1, R2, m, X und Z die unter Formel I gegebene Bedeutung haben, gegebenenfalls in Gegenwart einer Base, miteinem Amin der Formel V
Figure imgb0076
worin E, R3 und R4 die unter Formel I gegebene Bedeutung haben, umsetzt oder c) Sulfonamide der oben angegebenen Formel II gegebenenfalls in Gegenwart einer Base mit einem Isocyanat oder Isothiocyanat der Formel VI
Figure imgb0077
worin E, R3, R4 und Z die unter Formel I gegebenen Bedeutungen haben, umsetzt oder d) ein N-Phenylsulfonylcarbamat der Formel VII
Figure imgb0078
worin A, R1, R2, m und X die unter Formel I gegebene Bedeutung haben und R11 für Wasserstoff, Halogen, Nitro oder C1-C3-Alkyl steht, mit einem Amin der oben angegebenen Formel V umsetzt und gegebenenfalls in ihre Salze überführt, indem man einen Sulfonylharnstoff der Formel I mit einem Amin, einem Alkalimetall- oder Erdalkalimetallhydroxid oder einer quaternären Ammoniumbase umsetzt. 15. A process for the preparation of the compounds of formula I, claim 1, characterized in that a) a phenylsulfonamide of the formula II
Figure imgb0073
 wherein A, R 1 , R 2 , X and m have the meaning given under formula I, in the presence of a base with an N-pyrimidinyl or triazinyl carbamate of the formula
Figure imgb0074
 wherein E, R 3 , R 4 and Z have the meaning given under formula I and R 11 represents hydrogen, halogen, nitro or C 1 -C 3 alkyl, or b) a phenylsulfonyl isocyanate or isothiocyanate of the formula IV
Figure imgb0075
 wherein A, R 1 , R 2 , m, X and Z have the meaning given under formula I, optionally in the presence of a base, with an amine of formula V.
Figure imgb0076
 wherein E, R 3 and R 4 have the meaning given under formula I, or c) sulfonamides of the formula II given above, optionally in the presence of a base with an isocyanate or isothiocyanate of the formula VI
Figure imgb0077
 wherein E, R 3 , R 4 and Z have the meanings given under formula I, or d) an N-phenylsulfonyl carbamate of the formula VII
Figure imgb0078
 wherein A, R 1 , R 2 , m and X have the meaning given under formula I and R 11 represents hydrogen, halogen, nitro or C 1 -C 3 alkyl, reacted with an amine of the above formula V and optionally in their salts are converted by reacting a sulfonylurea of the formula I with an amine, an alkali metal or alkaline earth metal hydroxide or a quaternary ammonium base. 16. Die Verwendung der N-Phenylsulfonyl-N'-triazinyl- oder -pyrimidinyl-harnstoffe der Formel I oder sie enthaltender Mittel zur Bekämpfung unerwünschten Pflanzenwachstums.16. The use of the N-phenylsulfonyl-N'-triazinyl- or -pyrimidinyl-ureas of the formula I or agents containing them for combating undesirable plant growth. 17. Die Verwendung der N-Phenylsulfonyl-N'-triazinyl- oder -pyrimidinyl-harnstoffe der Formel I oder sie enthaltender Mittel zur Hemmung des Pflanzenwachstums.17. The use of the N-phenylsulfonyl-N'-triazinyl- or -pyrimidinyl-ureas of the formula I or agents containing them for inhibiting plant growth. 18. Die Verwendung gemäss Anspruch 16 zur selektiven pre- oder postemergenten Bekämpfung von Unkräutern in Nutzpflanzenkulturen.18. The use according to claim 16 for selective pre- or post-emergence control of weeds in crops. 19. Die Verwendung gemäss Anspruch 18 in Getreide-, Mais-, Reis-und Baumwollkulturen.19. The use according to claim 18 in cereals, maize, rice and cotton crops. 20. Die Verwendung gemäss Anspruch 18 in Sojakulturen.20. The use according to claim 18 in soybean crops. 21. Die Verwendung gemäss Anspruch 17, zur Unterdrückung des Pflanzenwachstums über das 2-Blattstadium hinaus, dadurch gekennzeichnet, dass die Wirkstoffe preemergent angewendet werden.21. The use according to claim 17, for the suppression of plant growth beyond the 2-leaf stage, characterized in that the active ingredients are used pre-allergenically. 22. Die Verwendung der N-Phenylsulfonyl-N'-triazinyl- oder -pyrimidinyl-harnstoffe der Formel I, Anspruch 1, oder sie enthaltender Mittel zur Wuchsregulierung von Kulturpflanzen zum Zwecke einer Ertragssteigerung. -22. The use of the N-phenylsulfonyl-N'-triazinyl- or -pyrimidinyl-ureas of the formula I, claim 1, or compositions containing them for regulating the growth of crop plants for the purpose of increasing the yield. - 23. Die Verwendung gemäss Anspruch 22.in Sojakulturen.23. The use according to claim 22 in soybean crops. 24. Die Verwendung gemäss Anspruch 17 bei Bodenbedecker-Leguminosen.24. The use according to claim 17 in ground cover legumes. 25. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es als Wirkstoff N-[2-(2-Chloräthoxy)-phenyl-sulfonyl]-N'-[4-methoxy-6-(2,2,2-trifluoräthoxy)-1,3,5-triazin-2-yl]-harnstoff.enthält.25. Composition according to claim 1, characterized in that it is active as N- [2- (2-chloroethoxy) phenylsulfonyl] -N '- [4-methoxy-6- (2,2,2-trifluoroethoxy) - 1,3,5-triazin-2-yl] urea. 26. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es als Wirkstoff N-(2-Trifluormethoxyphenyl-sulfonyl)-N'-(4-difluormethoxy-6-methyl-pyrimidin-2-yl)-harnstoff enthält.26. Composition according to claim 1, characterized in that it contains N- (2-trifluoromethoxyphenylsulfonyl) -N '- (4-difluoromethoxy-6-methyl-pyrimidin-2-yl) urea as active ingredient.
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US5244866A (en) * 1992-07-31 1993-09-14 American Cyanamid Company Method of inhibiting sprout growth on agronomic crops using acetohydroxy acid synthase inhibiting herbicides
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MA19609A1 (en) 1983-04-01
RO85266A (en) 1984-09-29
KR890002084B1 (en) 1989-06-16
MY8700843A (en) 1987-12-31
AU8677082A (en) 1983-02-10
US4545811A (en) 1985-10-08
DE3267431D1 (en) 1985-12-19
DD203223A5 (en) 1983-10-19
IL66460A0 (en) 1982-12-31
RO85266B (en) 1984-10-30
CS241510B2 (en) 1986-03-13
DK351182A (en) 1983-02-07
EG15835A (en) 1986-12-30
AU548397B2 (en) 1985-12-12
PH22230A (en) 1988-07-01
GR81400B (en) 1984-12-11
EP0072347B1 (en) 1985-11-13
ES8307761A1 (en) 1983-08-01
DK159433B (en) 1990-10-15
HU190702B (en) 1986-10-28
TR21767A (en) 1985-06-25
US4693741A (en) 1987-09-15
CA1231948A (en) 1988-01-26
ZW16082A1 (en) 1983-02-23
BR8204597A (en) 1983-07-26
CY1436A (en) 1989-03-10
DK159433C (en) 1991-03-18
CS580182A2 (en) 1985-08-15
KR840001149A (en) 1984-03-28
NZ201510A (en) 1985-11-08
ES514750A0 (en) 1983-08-01

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